Reworkable thermosetting resin composition

ABSTRACT

This invention relates to thermosetting resin compositions useful for mounting onto a circuit board semiconductor devices, such as CSPs, BGAs, LGAs and the like, each of which having a semiconductor chip, such as LSI, on a carrier substrate. The compositions of this invention are reworkable when subjected to appropriate conditions.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to thermosetting resin compositions useful forinstance, in mounting onto a circuit board semiconductor devices, suchas chip size or chip scale packages (“CSPs”), ball grid arrays (“BGAs”),land grid arrays (“LGAs”) and the like, each of which having asemiconductor chip, such as large scale integration (“LSI”), on acarrier substrate. The compositions of this invention are reworkablewhen subjected to appropriate conditions.

2. Brief Description of Related Technology

In recent years, the popularity of small-sized electronic appliances,such as camera-integrated video tape recorders (“VTRs”) and portabletelephone sets, has made size reduction of LSI devices desirable. As aresult, CSPs, BGAs and LGAs are being used to reduce the size ofpackages substantially to that of bare chips. Such CSPs, BGAs, LGAsimprove the characteristics of the electronic device while retainingmany of their operating features, thus serving to protect semiconductorbare chips, such as LSIs, and facilitate testing thereof.

Ordinarily, the CSP/BGA/LGA assembly is connected to electricalconductors on a circuit board by use of a solder connection or the like.However, when the resulting CSP/BGA/LGA/circuit board structure isexposed to thermal cycling, the reliability of the solder connectionbetween the circuit board and the CSP/BGA/LGA often becomes suspect.Recently, after a CSP/BGA/LGA assembly is mounted on a circuit board,the space between the CSP/BGA/LGA assembly and the circuit board isoften now filled with a sealing resin (often referred to as underfillsealing) in order to relieve stresses caused by thermal cycling, therebyimproving heat shock properties and enhancing the reliability of thestructure.

However, since thermosetting resins are typically used as the underfillsealing material, in the event of a failure after the CSP/BGA/LGAassembly is mounted on the circuit board, it is very difficult toreplace the CSP/BGA/LGA assembly without destroying or scrapping thestructure in its entirety.

To that end, techniques for mounting a bare chip on a circuit board areaccepted as substantially similar to the mounting of a CSP/BGA/LGAassembly onto a circuit board. One such technique, disclosed in JapaneseLaid-Open Patent Publication No. 102343/93, involves a mounting processwhere a bare chip is fixed and connected to a circuit board by use of aphotocurable adhesive, where, in the event of failure, this bare chip isremoved therefrom. However, this technique is limited to those instanceswhere the circuit board includes a transparent substrate (e.g., glass)which permits exposure to light from the back side, and the resultingstructure exhibits poor heat shock properties.

Japanese Laid-Open Patent Publication No. 69280/94 discloses a processwhere a bare chip is fixed and connected to a substrate by use of aresin capable of hardening at a predetermined temperature. In the eventof failure, this bare chip is removed from the substrate by softeningthe resin at a temperature higher than the predetermined temperature.However, no specific resin is disclosed, and there is no disclosureabout treating the resin which remains on the substrate. Thus, thedisclosed process is at best incomplete.

As pointed out in Japanese Laid-Open Patent Publication No. 77264/94, itis conventional to use a solvent to remove residual resin from a circuitboard. However, swelling the resin with a solvent is a time consumingprocess and the corrosive organic acid ordinarily used as the solventmay reduce the reliability of the circuit board. Instead, thatdisclosure speaks to a method for removing residual resin by irradiationwith electromagnetic radiation.

Japanese Laid-Open Patent Publication No. 251516/93 also discloses amounting process using bisphenol A type epoxy resin (CV5183 or CV5183S;manufactured by Matsushita Electric Industrial Co., Ltd.). However, theremoval process so disclosed does not consistently permit easy removalof the chip, the curing step is lengthy at elevated temperatures, andthe process generally results in poor productivity.

Of course, mechanical methods of removing/replacing semiconductor chipsfrom/on a substrate are known, such as by cutting the chip to beremoved/replaced. See U.S. Pat. No. 5,355,580 (Tsukada).

Thermoplastic underfill resins are known for use in semiconductor chipattachment. See U.S. Pat. No. 5,783,867 (Belke, Jr.). However, suchthermoplastic resins tend to leak under relatively modest temperatureconditions. In contrast, thermosetting resins cure into a matrix whichordinarily have greater thermal stability under end use operatingtemperatures.

U.S. Pat. No. 5,512,613 (Afzali-Ardakani), U.S. Pat. No. 5,560,934(Afzali-Ardakani) and U.S. Pat. No. 5,932,682 (Buchwalter), each referto a reworkable thermoset composition based on a diepoxide component inwhich the organic linking moiety connecting the two epoxy groups of thediepoxide includes an acid cleavable acyclic acetal group. With suchacid cleavable acyclic acetal groups forming the bases of the reworkablecomposition, a cured thermoset need only be introduced to an acidicenvironment in order to achieve softening and a loss of much of itsadhesiveness.

U.S. Pat. No. 5,872,158 (Kuczynski) and U.S. Pat. No. 6,008,266(Kuczynski), each refer to thermosetting compositions capable of curingupon exposure to actinic radiation, which are based on acetaldiacrylates and acetal diepoxides, respectively, and reaction productsof which are reported to be soluble in dilute acid.

U.S. Pat. No. 5,760,337 (Iyer) refers to thermally reworkablecrosslinked resins to fill the gap created between a semiconductordevice and a substrate to which it is attached. These resins areproduced by reacting a dienophile (with a functionality greater than 1)with a 2,5-dialkyl substituted furan-containing polymer.

International Patent Publication No. PCT/US98/00858 refers to athermosetting resin composition capable of sealing underfilling betweena semiconductor device including a semiconductor chip mounted on acarrier substrate and a circuit board to which said semiconductor deviceis electrically connected. The composition includes about 100 parts byweight of an epoxy resin, about 3 to about 60 parts by weight of acuring agent, and about 1 to about 90 parts by weight of a plasticizer.Here, the area around the cured thermoset is to be heated at atemperature of about 190 to about 260° C. for a period of time rangingfrom about 10 seconds to about 1 minute in order to achieve softeningand a loss of much of its adhesiveness.

U.S. Pat. No. 5,948,922 (Ober) and U.S. Pat. No. 5,973,033 (Ober), eachrefer to a certain class of compounds having tertiary oxycarbonyllinkages, and compositions based on such compounds, which when curedprovide thermally decomposable compositions capable of being reworked.

Notwithstanding the state of the art, it would be desirable for anunderfilling sealing material to provide good productivity, thermalshock and mechnaical stress absorbing properties, while allowing thesubstrates with which it is to be used to be readily processed andeasily separated from a semiconductor device without application of tooextreme conditions that may compromise the integrity of thesemiconductor devices remaining on the substrate or the substrateitself. In addition, it would be desirable to provide such a materialwhich is based on an epoxy material for reworkability that may beprepared from readily available and inexpensive starting materials.

SUMMARY OF THE INVENTION

The present invention provides a thermosetting resin composition, whichincludes broadly a curable resin component, at least a portion of whichis a compound having at least one linkage selected from oxiranes,thiiranes, and combinations thereof, substituted on at least three ofthe substitutable positions on the oxirane and/or thiirane carbons,respectively, with an alkyl, alkenyl or aryl substituent having a carboncontent of one to about twelve carbon atoms, with or withoutsubstitution or interruption by one or more heteroatoms or halogens, asappropriate; and a curing agent component including an anhydridecomponent, a nitrogen-containing component, such as amine or azacompounds, amide compounds, and/or imidazole compounds, or combinationsthereof.

The present invention also provides novel diepoxide-containingcompounds, the structures for which are described in detail herein.

Reaction products of these compositions are capable of softening underexposure to elevated temperature conditions, such as in excess of thetempertures used to cure the composition. Such temperature exposureprovides the reworkable aspect of the reaction products of the inventivecompositions. The remaining components, discussed below, provide thephysical properties and characteristics for the compositions andreaction products to render the compositions attractive for commercialuse, particularly in the microelectronics industry.

The inventive compositions are useful as an underfilling sealing resin,and enables a semiconductor device, such as a CSP/BGA/LGA assembly whichincludes a semiconductor chip mounted on a carrier substrate, to besecurely connected to a circuit board by short-time heat curing and withgood productivity. Reaction products of the inventive compositionsdemonstrate excellent heat shock properties, and permit thesemiconductor device to be easily removed from the circuit board bylocalized heating in excess of the temperature at which the composioncures, in the event of semiconductor device or connection failure. Thismakes it possible to reuse the circuit board (with the remainingfunctioning semiconductor devices still electrically attached) andthereby achieve an improvement in the yield of the production processand a reduction in production cost.

The compositions of this invention may also be used for microelectronicapplications beyond sealing underfill, such as with glob top, dieattachment and other applications for thermosetting compositions.

Other benefits and advantages of the present invention will become morereadily apparent after a reading of the “Detailed Description” sectiontogether with the figures.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a cross-sectional view showing an example of the mountingstructure in which the thermosetting resin composition of the presentinvention is used.

FIG. 2 depicts a flow diagram of a procedure useful to rework a curedthermosetting resin composition in accordance with the presentinvention, so as to remove a semiconductor device from a circuit boardto which it had been attached.

FIG. 3 depicts a TGA curve of cured reaction products of compositionsbased on limonene diepoxide (square), Compound XVI of U.S. Pat. No.5,948,922 (Ober) and U.S. Pat. No. 5,973,033 (Ober)(circle),commercially available diepoxidized dicycloaliphatic ester (ERL4221)(closed square) and commercially available diglycidyl ether ofbisphenol F epoxy resin (RE-404-S)(asterisk), cured with an anhydridecuring agent.

FIG. 4 depicts a TGA curve of cured reaction products of compositionsbased on terpinene diepoxide (square), Compound XVI of the '922 and '033patents (circle), ERL 4221 (closed square) and RE-404-S (asterisk),cured with an anhydride curing agent.

FIG. 5 depicts a TGA curve of cured reaction products of compositionsbased on limonene diepoxide and RE-404-S at different ratios, andRE-404-S (asterisk), cured with an imidazole/dicyandiamide curing agent.

FIG. 6 depicts a TGA curve of cured reaction products of compositionsbased on limonene diepoxide/RE-404-S (circle), Compound XVI of the '922and '033 patents (square), ERL 4221 (diamond) and RE-404-S (asterisk),cured with an imidazole/dicyandiamide curing agent.

FIG. 7 depicts a TGA curve of cured reaction products of compositionsbased on gamma-terpinene diepoxide and RE-404-S at different ratios, andRE-404-S (asterisk), cured with an imidazole/dicyandiamide curing agent.

FIG. 8 depicts a TGA curve of cured reaction products of compositionsbased on gamma-terpinene diepoxide/RE-404-S (circle), Compound XVI ofthe '922 and '033 patents (square), ERL 4221 (diamond) and RE-404-S,cured with an imidazole/dicyandiamide curing agent.

FIG. 9 depicts a TGA curve of cured reaction products of compositionsbased on methyl cyclopentadiene dimer diepoxide and RE-404-S atdifferent ratios, and RE-404-S (asterisk), cured with an anhydridecuring agent.

FIG. 10 depicts a TGA curve of cured reaction products of compositionsbased on methyl cyclopentadiene dimer diepoxide (circle), Compound XVIof the '922 and '033 patents (square), ERL 4221 (diamond) and RE-404-S(asterisk), cured with an anhydride curing agent.

FIG. 11 depicts a TGA curve of cured reaction products of compositionsbased on ethylidene norbornene diepoxide and RE-404-S at differentratios, and RE-404-S (asterisk), cured with an anhydride curing agent.

FIG. 12 depicts a TGA curve of cured reaction products of compositionsbased on ethylidene norbornene diepoxide (circle), Compound XVI of the'922 and '033 patents (square), ERL 4221 (diamond) and RE-404-S, curedwith an anhydride curing agent.

FIG. 13 depicts a TGA curve of cured reaction products of compositionsbased on nopol epoxide glycidyl ether and RE-404-S at different ratios,and RE-404-S (asterisk), cured with an anhydride curing agent.

FIG. 14 depicts a TGA curve of cured reaction products of compositionsbased on nopol epoxide glycidyl ether (circle), Compound XVI of the '922and '033 patents (square), ERL 4221 (diamond) and RE-404-S, cured withan anhydride curing agent.

FIG. 15 depicts a ¹H HMR spectra of nopol glycidyl ether.

FIG. 16 depicts a FT-IR spectra of nopol glycidyl ether.

FIG. 17 depicts a ¹H HMR spectra of nopol epoxide glycidyl ether.

FIG. 18 depicts a FT-IR spectra of nopol epoxide glycidyl ether.

DETAILED DESCRIPTION OF THE INVENTION

As noted above, the thermosetting resin compositions are useful forinstance in microelectronic assembly applications, such as underfillsealants between a semiconductor device and a circuit board to which thesemiconductor device is electrically connected. Of course, thecompositions may also be used for other microelectronic assemblyapplications, such as the direct chip attach applications, includingglob top, and dam and fill. In addition, the compositions may be used infar-flung applications, where thermosetting epoxies, or for that matterother thermosetting or thermoplastic adhesive, coating and sealantcompositions, may be used.

For instance, the compositions may be used in the assembly of products,whose component parts have value as do the intermediate/finishedproducts, to facilitate assembly and disassembly thereof where defectivecomponent parts are found. In that event, the defective componentpart(s) may be readily removed from the intermediate/finished product(s)and be replaced without having to scrap the entire intermediate/finishedproduct(s). In addition, the speed with which the disassembly mayproceed allows throughput to remain high. A non-microelectronic exampleof such a part is the assembly of prosthetic devices.

The composition includes broadly (a) an epoxy resin component, at leasta portion of which is a compound (I) having at least one linkageselected from oxiranes, thiiranes, and combinations thereof, substitutedon at least three of the substitutable positions on the oxirane and/orthiirane carbons, respectively, with an alkyl, alkenyl or arylsubstituent having a carbon content of 1 to about twelve carbon atoms,with or without substitution or interruption by one or more heteroatomsor halogens, as appropriate, provided that the compound I does notinclude as its sole component an epoxy compound within formula II:

wherein each R is independently selected from the group consisting ofhydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl,C₁₋₄ alkoxy, halogen, cyano and nitro, R₁ and R₂ are each independentlyselected from the group consisting of hydrogen, methyl, ethyl, andpropyl, provided that both R₁ and R₂ cannot be hydrogen, and R₃ isindependently selected from propyl, and isopropyl, provided at least oneof R_(3a) and R_(3b), and at least one of R₃, and R_(3d) isindependently selected from the group consisting of methyl, ethyl,propyl, and isopropyl, and m is 0 or 1.0 and (b) a curing agentcomponent selected from anhydride compounds, amine compounds, amidecompounds, imidazole compounds, and combinations thereof.

Reaction products of these compositions are capable of softening underexposure to elevated temperature conditions, such as in excess of thetemperature chosen to cure the composition. Loss of adhesion to thesubstrate occurs at temperatures greater than that which was used tocure the composition. For instance, at least about 50% of adhesion tothe substrate is typically lost at temperatures in excess of about 200°C.

Typically, the composition includes about 10 to about 70 weight percentof the curable resin component, such as about 15 to about 60 weightpercent, desirably about 30 to about 50 weight percent, based on theweight of the total composition, of which about 25 to about 75 weightpercent, such as about 35 to about 65 weight percent, desirably about 45to about 55 weight percent, is comprised of a compound having at leastone linkage selected from oxiranes, thiiranes, and combinations thereof,substituted on at least three of the substitutable positions on theoxirane and/or thiirane carbons, respectively, with an alkyl, alkenyl oraryl substituent having a carbon content of 1 to about twelve carbonatoms, with or without substitution or interruption by one or moreheteroatoms or halogens; and 1 to about 100 weight percent of the curingagent component, based on the total weight of the curable resincomponent, depending of course on the type and identity of the curingagent chosen.

Of course, depending on the particular set of properties desirable for acomposition destined for a specific purpose these values may varysomewhat. Such variation may be achieved without undue experimentationby those persons skilled in the art, and accordingly are contemplatedwithin the scope of the present invention.

The curable resin component of the present invention may include anycommon epoxy resin, such as a multifunctional epoxy resin. Ordinarily,the multifunctional epoxy resin should be included in an amount withinthe range of about 10 weight percent to about 80 weight percent, such asabout 15 to about 75 weight percent, desirably about 25 to about 60weight percent, of the total of the epoxy resin component. In the caseof bisphenol-F-type epoxy resin, desirably the amount thereof should bein the range of from about 15 to about 60 weight percent, such as about30 to about 50 weight percent, based on the weight of the curable resincomponent.

Examples of the multifunctional epoxy resin include bisphenol-A-typeepoxy resin, bisphenol-F-type epoxy resin (diglycidyl ether ofbisphenol-F-type epoxy resin, such as RE-404-S from Nippon Kayaku,Japan), phenol novolac-type epoxy resin, and cresol novolac-type epoxyfrom resin (such as “ARALDITE” ECN 1871 from Ciba Specialty Chemicals,Hawthorne, N.Y.).

Other suitable epoxy resins include polyepoxy compounds based onaromatic amines and epichlorohydrin, such asN,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenyl methane;N-diglycidyl-4-aminophenyl glycidyl ether; andN,N,N′,N′-tetraglycidyl-1,3-propylene bis-4-aminobenzoate.

Among the epoxy resins suitable for use herein also include polyglycidylderivatives of phenolic compounds, such as those available commerciallyunder the tradename “EPON”, such as “EPON” 828, “EPON” 1001, “EPON”1009, and “EPON” 1031 from Shell Chemical Co.; “DER” 331, “DER” 332,“DER” 334, and “DER” 542 from Dow Chemical Co.; and “BREN-S” from NipponKayaku. Other suitable epoxy resins include polyepoxides prepared frompolyols and the like and polyglycidyl derivatives of phenol-formaldehydenovolacs, the latter of which are available commercially under thetradename “DEN”, such as “DEN” 431, “DEN” 438, and “DEN” 439 from DowChemical. Cresol analogs are also available commercially under thetradename “ARALDITE”, such as “ARALDITE” ECN 1235, “ARALDITE” ECN 1273,and “ARALDITE” ECN 1299 from Ciba Specialty Chemicals. SU-8 is abisphenol-A-type epoxy novolac available from Interez, Inc. Polyglycidyladducts of amines, aminoalcohols and polycarboxylic acids are alsouseful in this invention, commercially available resins of which include“GLYAMINE” 135, “GLYAMINE” 125, and “GLYAMINE” 115 from F.I.C.Corporation; “ARALDITE” MY-720, “ARALDITE” 0500, and “ARALDITE” 0510from Ciba Specialty Chemicals and PGA-X and PGA-C from theSherwin-Williams Co.

Still other epoxy resins that are suitable for use herein includealiphatic epoxies with alkylene oxide residues, examples of whichinclude, but are not limited to, mono-, di- or multi-functional epoxiescontaining ether linkages, such as primary, secondary and tertaryalkylene diol diglycidyl ethers, and epoxies containing mono- orpoly-alkylene oxide residues (such as ethylene oxide, propylene oxide,butylene oxide, pentylene oxide, and hexylene oxide residues).

For instance,

where n is an integer from 1 to about 18, are each appropriate,individually or in combination, for use as at least a portion of theepoxy resin component.

Examples of cycloaliphatic epoxies with alkylene oxide residues includemono-, di- or multi functional cyclohexyl epoxies; hydrated bisphenolA-type epoxies; and hydrated bisphenol F-type epoxies, containingalkylene ether residues. DME-100 (1,4-cyclohexane dimethanol diglycidylether, available commercially from New Japan Chemical Co., Ltd.) asshown below is one such example.

Examples of aromatic epoxies with alkylene oxide residues include mono-,di- or multi-functional epoxies such as bisphenol A type epoxies;bisphenol F type epoxies; phenol novolac type epoxies; and cresolnovolac type epoxies, containing alkylene ether residues.

Examples of such epoxies include BEO-60E (ethoxylated bisphenol Adi-glycidyl ether, available

commercially from New Japan Chemical Co., Ltd.), and BPO-20E(propyloxylated bisphenol A di-glycidyl ether, available commerciallyfrom New Japan Chemical Co., Ltd.), which are shown below:where n is an integer between and about 1 and 20, which for BPO-60E n is1, and

where n is an integer between and about 1 and 20, which for BEO-60E n is3.

And of course combinations of the different epoxy resins are alsodesirable for use herein.

The inventive composition, which after cure lends itself to being“reworked” under appropriate conditions, includes a compound having atleast one oxirane or thiirane linkage substituted on at least three ofthe substitutable positions on the oxirane or thiirane carbons,respectfully, with an alkyl, alkenyl or aryl substituent having a carboncontent of 1 to about twelve carbon atoms, with or without substitutionor interuption by one or more heteroatoms or halogens. When reacted witha curing agent it is believed that these oxirane or thiirane compoundsform a tertiary ester (when the curing agent is anhydride based) or atertiary ether (when the curing agent is nitrogen-based, such as with animidazole), which linkage is susceptible to controlled degradation underappropriate conditions, such as elevated temperature and/or acidicenvironment.

Particular examples of such compounds include di- or poly-oxirane andthiirane compounds prepared from2,10-dimethyl-6-methylene-4,8-bis(2-methyl-1-propenyl-2,4,7,9-undecatetraene(CAS Reg. No. 249664-51-7), 4-[(4E or 4Z)-1,5-dimethyl-4-heptenylideneor octenylidene]-1-methyl-cyclohexene (CAS Reg. Nos. 221269-56-3,221269-55-2, 209462-40-8, 209462-39-5), 1,1′-[(1E or 1Z, 3E or3Z)-5-(1,1-dimethyl-2-propenyl)-3-(3-methyl-2-butenyl)-1,3-pentadiene-1,5-diyl]bis-benzene(CAS Reg. No. 207513-40-4), 4,6-dimethyl-[S or R-(E or Z, Z orE)]-2,5-octadiene (CAS Reg. No. 203515-58-6, 203515-52-0),2,6,10,14-tetramethyl-7-(3-methyl-4-pentenyl)-2,5,9,13-pentadecatetraene(CAS Reg. No. 202134-68-7), 7-ethyl-3,11-dimethyl-(3Z or 3E, 6E or 6Z,10Z or 10E)-1,3,6,10-tridecatetraene (CAS Reg. No. 189387-61-9),3,4,8-trimethyl-1,4,7-nonatriene (CAS Reg. No. 179981-39-6),13-ethyl-9-methyl-1,9,12-pentadecatetraene (CAS Reg. No. 174189-19-6),1-methyl-4-(2-methyl-6-heptenylidene)-cyclohexene (CAS Reg. No.170274-84-7), 2,6,11-trimethyl-(E or Z)-2,5,10-dodecatriene (CAS Reg.No. 169524-63-4), 2,6-dimethyl-(E or Z, E or Z)-2,6,9-tetradecatriene(CAS Reg. No. 169265-90-1), 7-(3-methyl-2-butenyl-(E or Z)-6-dodecene(CAS Reg. No. 168141-30-8), 6-(3-methyl-2-butenyl)-(E or Z)-6-dodecene(CAS Reg. No. 168141-25-1), 2,4,6,6,8-pentamethyl-2,4,7-nonatriene (CASReg. No. 164993-09-9), 3,7-dimethyl-11-(methyl)-(E or Z, E orZ)-1,3,6,10-dodecatetraene (CAS Reg. No. 162189-16-4),5-[3-methyl-1-(2-methyl-1-propenyl)-2-butenylidene]-1,3-cyclopentadiene(CAS Reg. No. 162143-83-1), 4-[(4E or4Z)-1,5-dimethyl-4-heptenylidene]-1-methyl-(4Z or 4E)-cyclohexene (CASReg. No. 160359-81-9), 3,7,11-trimethyl-1,3,6,10-docosatetraene (CASReg. No. 159085-88-8), 3,7,11,15-tetramethyl-1,3,6,10-hexadecatetraene(CAS Reg. No. 158729-00-1), 9-ethyl-2,6-dimethyl-(E or Z, E orZ)-2,6,9-dodecatriene (CAS Reg. No. 157337-30-9), 2-methyl-5-propyl-(Eor Z)-2,5-nonadiene (CAS Reg. No. 157337-25-2), 3,7,11-trimethyl-(Z orE, E or Z, E or Z)-1,3,6,10-dodecatetraene (CAS Reg. Nos. 154579-52-9,154579-50-7, 154579-49-4, 154579-40-5), 4,8,12-trimethyl-(Z or E, E orZ, E)-2,4,7,11-tridecatetraene (CAS Reg. Nos. 154579-51-8, 154579-47-2),1-methyl-4-(2-methyl-6-heptenylidene)-(E or Z)-cyclohexene (CAS Reg. No.152252-96-5), 3-ethyl-7,11-dimethyl-(E or Z, E or Z)-1, 3, 6,10-dodecatetraene (CAS Reg. No. 152195-83-0),2,6,6,9-tetramethyl-7-(2-methyl-1-propenyl)-2,4,8-decatriene (CAS Reg.No. 150280-97-0),2,7-dimethyl-4,5-bis(2-methyl-1-propenyl)-2,6-octadiene (CAS Reg. No.150280-96-9), 3,7-dimethyl-1,3,6-octatriene (CAS Reg. No. 147727-60-4),2-methyl-5-(1-methylethylidene)-cyclohexene (CAS Reg. No. 147727-51-3),2,6-dimethyl-5-(1-methylethylidene)-1,3-cyclohexadiene (CAS Reg. No.138434-36-3), 2,6-dimethyl-2,5-decadiene or octadiene (CAS Reg. Nos.134956-14-2, 128144-73-0), 7-ethyl-3,11-dimethyl-1,3,6,10-dodecatetraene(CAS Reg. No. 134779-29-6), 2-methyl-(E or Z)-2,5-octadiene (CAS Reg.No. 133797-14-5), 7-ethyl-3,11-dimethyl-(E or Z, E orZ)-1,3,6,10-dodecatetraene (CAS Reg. No. 127941-96-2),2,7,11-trimethyl-(E or Z)-2,5,10-dodecatriene (CAS Reg. No.124745-43-3), 6,10-dimethyl-(Z or E, Z or E)-2,6,9-undecatrien-4-yne(CAS Reg. No. 122305-03-7), 2,6-dimethyl-(Z or E)-2,5-dodecadiene (CASReg. No. 121403-30-3),2,7-dimethyl-4,5-bis(2-methyl-1-propenyl)-2,4,6-octatriene (CAS Reg. No.117712-68-2), 2,3,6,7-tetramethyl-1,3,6-octatriene (CAS Reg. No.117527-68-1), 2-methyl-5-propyl-(Z or E)-2,5-dodecadiene (CAS Reg. No.116893-95-9), 2-methyl-5-(1-methylethyl)-(E or Z)-2,5-dodecadiene (CASReg. No. 116893-93-7), 2-methyl-(Z or E)-2,5-dodecadiene (CAS Reg. No.116893-92-6), 2,4,4-trimethyl-(E or Z)-2,5-heptadiene (CAS Reg. No.116786-15-3), 2,6-dimethyl-2,5-octadiene (CAS Reg. No. 116668-48-5),3,4,7,11-tetramethyl- (E or Z, Z or E)-1,3,6,10-dodecatraene (CAS Reg.Nos. 114091-33-7, 114091-32-6), 3,7,11-trimethyl-(E or Z, E orZ)-1,3,6,10-dodecatetraene (CAS Reg. No. 113244-64-7),4,8-dimethyl-1,4,7-nonatriene (CAS Reg. No. 110559-67-6),3,7,11,15-tetramethyl-1,3,6,10,14-hexadecapentaene (CAS Reg. No.110249-03-1), 2-methyl-(Z or E)-2,5-pentadecadiene (CAS Reg. Nos.108181-16-4, 108181-15-3), 2-methyl-5-(1-methylethylidene)-2-decene (CASReg. No. 107909-37-5), 2,6-dimethyl-2,5,7-decatriene (CAS Reg. No.105694-90-4), 4,8-dimethyl-2,4,7-nonatriene (CAS Reg. No. 105694-88-0),15,19,23-trimethyl-15,18,22-heptatriacontatriene (CAS Reg. No.104519-12-2), 8-(2-methyl-1-propenyl)-6-tetradecene (CAS Reg. No.10229-83-2), 3,7,11-trimethyl-(E or Z)-1,3,6,10-dodecatetraene (CAS Reg.No. 97885-54-6), 3,4-didehydro-2-(3-methyl-2-butenyl)-carotene (CAS Reg.No. 97231-43-1), 7-ethyl-3,11-dimethyl-1,3,6,10-dodecatetraene (CAS Reg.No. 96890-21-0), 1,3-dimethyl-4-propylidene-cyclopentene (CAS Reg. No.96095-54-4), 2,7,11-trimethyl-(E or Z, E or Z)-1,3,6,10-dodecatetraene(CAS Reg. No. 93517-88-5), 6,10-dimethyl-1,4,6,9-undecatetraene (CASReg. No. 93308-70-4),2-(1-methylethyl)-5-(1-methylethylidene)-1,3-cyclohexadiene (CAS Reg.No. 92545-19-2), 2-ethyl-5-ethylidene-cyclohexadiene (CAS Reg. No.92545-18-1), 2-methyl-5-(1-methylethylidene)-1,3-cyclohexadiene (CASReg. No. 92545-16-9), 3,7,10-trimethyl-(Z or E, E orZ)-1,3,6-undecatriene (CAS Reg. No. 91203-72-4),4-(1,5-dimethyl-4-hexenylidene)-1-methyl-cyclohexene (CAS Reg. No.90458-95-0), 1-methyl-4-(1-methylethylidene)-cyclohexene (CAS Reg. No.83259-95-4), 2,5-dimethyl-(Z or E)-2,5-heptadiene (CAS Reg. Nos.83180-40-9, 83180-39-6),2-methyl-5-(1-methylethylidene)-1,3-cyclohexadiene (CAS Reg. No.81719-66-6), 2,6,10-trimethyl-(E or Z, Z or E)-2,6,9-tetradecatriene(CAS Reg. No. 80873-82-1), 6-methyl-(Z or E, E or Z)-2,5-dodecadiene(CAS Reg. Nos. 80873-79-6, 80873-78-5), 2,3,6-trimethyl-(E or Z, E orZ)-1,3,6-octatriene (CAS Reg. No. 80651-22-5),tetrahydro-3,7,11-trimethyl-1,3,6,10-dodecatetraene (CAS Reg. No.80338-47-2), 3,4,7,11-tetramethyl-1,3,6,10-dodecatetraene (CAS Reg. No.7983-34-9), 3,4,7,11-tetramethyl-(Z or E, Z orE)-1,3,6,10-dodecatetraene (CAS Reg. No. 79383-33-8),2,6-dimethyl-4-methylene-2,5-heptadiene (CAS Reg. No. 77832-43-6),5-ethyl-2-methyl-2,5-heptadiene (CAS Reg. No. 78811-91-3),2,5-dimethyl-2,5-heptadiene or octadiene (CAS Reg. Nos. 78811-90-2,78811-89-9), 3,7,11-trimethyl-dodecatriene (CAS Reg. No. 78339-48-7),2,4,6,6,8-pentamethyl-(E or Z)-2,4,7-nonatriene (CAS Reg. No.78310-14-2), 3,7-diethyl-11-methyl-1,3,6,10-tridecatetraene (CAS Reg.No. 78216-57-6), 7-ethyl-3,11-dimethyl-1,3,6,10-tridecatetraene (CASReg. No. 78183-46-7), 2,6-dimethyl-(E or Z)-2,5-dodecadiene (CAS Reg.No. 77958-38-4), 2,6,10-trimethyl-(E or Z, E or Z)-2,6,9-tetradecatriene(CAS Reg. No. 77958-36-2), 3,7,11,15-tetramethyl-(Z or E, E or Z, E orZ)-1,3,6,10,14-hexadecapentaene (CAS Reg. No. 77898-98-7),3,7,11,15-tetramethyl-(3E or 3Z, 6E or 6Z, 10E or10Z)-1,3,6,10,14-hexadecapentaene (CAS Reg. No. 77898-97-6),1-ethenyl-4-(1-methylethylidene)-cyclohexene (CAS Reg. No. 77142-28-0),1-methyl-6-methylene-4-(1-methylethylidene)-cyclohexene (CAS Reg. No.77142-23-5), 3,7,11-trimethyl-1,3,6-dodecatriene (CAS Reg. No.74253-06-8), 4-(1,5-dimethylhexylidene)-1-methyl-cyclohexene, (CAS Reg.No. 74253-05-7), 7-ethyl-3,11-dimethyl-(3Z or 3E, 6E or6Z)-1,3,6,10-dodecatetraene (CAS Reg. No. 73690-00-3),1,3,3′,4,4′,16-hexadehydro-1,2-dihydro-2,2′-bis(3-carotene (CAS Reg. No.77365-74-9), 7-methyl-(Z or E, Z or E)-3,6-dodecadiene (CAS Reg. Nos.72858-64-1, 72858-63-0), 6-ethylidene-2,3,10-trimethyl-(E or Z, E orZ)-1,3,9-undecatriene (CAS Reg. No. 72564-39-7),2,3,6,7,10,11-hexamethyl-(E or Z, E or Z)-1,3,6,10-dodecatetraene (CASReg. No. 72564-36-4), 2,3,6,7-tetramethyl-(E or Z)-1,3,6-octatriene (CASReg. No. 72564-35-3), 2,7,11-trimethyl-1,3,6,11-dodecatetraene (CAS Reg.No. 71803-35-5),3,7,11,15,19,23,27,31,35-nonamethyl-1,3,6,10,14,18,22,26,30,34-hexatriacontadecaene(CAS Reg. No. 71278-21-2), 2,6-dimethyl-9-propyl-2,6,9-tridecatriene(CAS Reg. No. 70602-78-7), 3,6-dimethyl-(E or Z, E orZ)-1,3,6-octatriene (CAS Reg. No. 70569-76-5), 3,7-diethyl-11-methyl-(3Zor 3E, 6E or 6Z) 1,3,6,10-tridecatetraene (CAS Reg. No. 70239-70-2),7-ethyl-3,11-dimethyl-(3Z or 3E, 6E or 6Z)-1,3,6,10-tridecatetraene (CASReg. No. 70234-77-4), 1-methyl-4-(5-methyl-4-hexenylidene)-(4E or4Z)-cyclohexene (CAS Reg. No. 66916-06-9), 2,6,10-trimethyl-(Z orE)-2,5,9-undecatriene (CAS Reg. Nos. 68974-97-0, 68974-96-9),2,6,7,7-tetramethyl-(Z or E)-2,5-octadiene (CAS Reg. Nos. 68974-95-8,68974-94-7), 2,6,10,11,11-pentamethyl-2,6,9-dodecatriene (CAS Reg. No.68965-68-4), 2,6,10-trimethyl-2,6,9-tetradecatriene (CAS Reg. No.68965-67-3), 2,6-dimethyl-(Z or E)-2,5-decadiene (CAS Reg. Nos.68965-66-2, 68965-65-1), 6,10-dimethyl-1,6,9-undecatrien-4-yne (CAS Reg.No. 68483-39-6), 2,3,6-trimethyl-2,5-heptadiene (CAS Reg. No.67796-57-0), 2,4-dimethyl-(E or Z)-2,5-heptadiene (CAS Reg. No.67796-55-8), 2,7,11-trimethyl-(E or Z, E or Z)-1,3,6,11-dodecatetraene(CAS Reg. No. 67023-83-0), 6-ethyl-3-methyl-2,5-decadiene (CAS Reg. No.65668-94-2), 2,6,10-trimethyl-(Z or E)-2,5-undecadiene (CAS Reg. Nos.64583-07-9, 64583-04-6), 3,7-dimethyl-3,6-octadien-1-yne (CAS Reg. No.64547-65-5), 2,7,10-trimethyl-1,6,9-undecatriene (CAS Reg. No.61058-91-1), 4,5-dimethyl-(E or Z, E or Z, E or Z)-3,5,8-undecatriene(CAS Reg. No. 59681-86-6), 4,5-dimethyl-2,5,8-undecatriene (CAS Reg. No.59681-84-4),1′-[4-methyl-2-(2-methyl-1-propenyl)-1,3-pentadienylidene]bis-benzene, 1(CAS Reg. No. 55861-06-8), 4-(1,5-dimethyl-4-hexenylidene)-1-methyl-(4Eor 4Z)-cyclohexene (CAS Reg. No. 53585-13-0), 2,6,11,15-tetramethyl-(Zor E)-2,6,9,14-hexadecatetraene (CAS Reg. Nos. 53254-62-9, 53254-61-8),[3-methyl-1-(2-methyl-1-propenyl)-2-butenyl]-benzene (CAS Reg. No.53210-24-5), 2,6,11-trimethyl-(E or Z, E or Z)-2,6,9-dodecatriene (CASReg. No. 51795-79-0), 2,6-dimethyl-(E or Z, E or Z)-2,6,9-dodecatriene(CAS Reg. No. 51795-74-5),2,3,6,7,10,11-hexamethyl-1,3,6,11-dodecatetraene (CAS Reg. No.45214-38-8),19-methyl-1-(2-methyl-1-2,4,6,8,10,12,14,16,18-eicosanonaenylium (CASReg. No. 40544-26-1),17-methyl-1-(2-methyl-1-propenyl)-2,4,6,8,10,12,14,16-octadecaoctaenylium(CAS Reg. No. 40544-25-0),15-methyl-1-(2-methyl-1-propenyl)-2,4,6,8,10,12,14-hexadecaheptaenylium(CAS Reg. No. 40544-24-9),13-methyl-1-(2-methyl-1-propenyl)-2,4,6,8,10,12-tetradecahexaenylium(CAS Reg. No. 40544-23-8),11-methyl-1-(2-methyl-1-propenyl)-2,4,6,8,10-dodecapentaenylium (CASReg. No. 40544-22-7),9-methyl-1-(2-methyl-1-propenyl)-2,4,6,8-decatetraenylium (CAS Reg. No.40544-21-6), 7-methyl-1-(2-methyl-1-propenyl)-2,4,6-octatrienylium (CASReg. No. 40544-20-5), 4,ethylidene-2,6-dimethyl-2,5-heptadiene (CAS Reg.No. 39117-23-2), 3,7,11-trimethyl-(E or Z)-3,6,11-dodecatrien-1-yne (CASReg. No. 36629-58-0), 3,7-dimethyl-(3E or 3Z)-3,6-octadien-1-yne (CASReg. Nos. 36602-32-1, 36602-31-0), 3,7-dimethyl-(E orZ)-3,6-nonadien-1-yne (CAS Reg. Nos. 36597-67-8, 36597-66-7),3,6,7-trimethyl-(E or Z)-3,6-octadien-1-yne (CAS Reg. Nos. 36597-64-5,36957-63-4), 7-ethyl-3-methyl-(E or Z)-3,6-nonadien-1-yne (CAS Reg. Nos.36597-61-2, 36597-60-1), 3,7,11-trimethyl-(Z orE)-3,6,11-dodecatrien-1-yne (CAS Reg. Nos. 36597-58-7, 36597-56-5,36597-56-4), 2,3,6,7,10,11-hexamethyl-1,3,6,11-dodecatetraene (CAS Reg.No. 34888-55-6), 2,6-dimethyl-2,5-heptadiene (CAS Reg. No. 34484-31-6),2-methyl-2,5-heptadiene (CAS Reg. No. 34484-29-2),3,6,10-trimethyl-2,5,7,10-dodecatetraene (CAS Reg. No. 32945-35-0),2,7,10-trimethyl-1,3,7,10-dodecatetraene (CAS Reg. No. 32925-31-8),3,6-dimethyl-1,3,6-octatriene (CAS Reg. No. 32778-25-9),12-(2,2-dimethyl-6-methylenecyclohexyl)-3,8,8-trimethyl-11-methylene-(Eor Z)-(S)-1,3,6-dodecatriene (CAS Reg. No. 29738-44-1), ocimene (CASReg. No. 29223-32-3), 3,7,11-trimethyl-,(3Z or 3E, 6Z or6E)-1,3,6,10-dodecatetraene (CAS Reg. Nos. 28973-99-1, 28973-98-0,26560-14-5), 2-methyl-4-methylene-2,5-heptadiene (CAS Reg. No.24498-9-5), 3,8,8,14,18-pentamethyl-11-methylene-(E orZ)-1,3,6,13,17-nonadecapentaene (CAS Reg. No. 23192-59-8),2,7-dimethyl-2,5-octadiene (CAS Reg. No. 20733-73-7),3,8,8,14,18-pentamethyl-11-methylene-(E or Z, E or Z, E orZ)-1,3,6,13,17-nonadecapentaene (CAS Reg. No. 19953-95-8),6,10-dimethyl-2,4,6,9-undecatetraene (CAS Reg. No. 19048-50-1),2-methyl-(Z or E)-2,5-heptadiene (CAS Reg. No. 18316-09-1), 2-methyl-(Eor Z)-2,5-heptadiene (CAS Reg. No. 18316-08-0),3,7-dimethyl-1,3,6-octatriene (CAS Reg. No. 13877-91-3),4-(1,5-dimethyl-4-hexenylidene)-1-methyl-(4Z or 4E)-cyclohexene (CASReg. No. 13062-00-5),2,6,10,14,19,22,27,31-octamethyl-2,6,10,14,16,18,22,26,30-dotriacontanonaene(CAS Reg. No. 13050-81-2), 2,6-dimethyl-2,5-heptadiene (CAS Reg. No.6090-16-0), 4-(1,5-dimethyl-4-hexenylidene)-1-methyl-cyclohexene (CASReg. No. 5957-36-8), 3,7-dimethyl-(3E or 3Z)-1,3,6-octatriene (CAS Reg.No. 3779-61-1),2,6,10,14,19,23,31-heptamethyl-2,5,10,14,16,18,22,26,29-dotriacontanonaene(CAS Reg. No. 3625-51-2), 3,7,dimethyl-(3Z or 3E)-1,3,6-octatriene (CASReg. No. 3338-55-4), 3-methyl-1-(2-methyl-1-propenyl-(E or Z)-2-pentenyl(CAS Reg. No. 3229-66-1),2,6-dimethyl-4-(2-methylpropenyl)-1,3,5-heptatriene (CAS Reg. No.1606-44-6), 2,6-dimethyl-4-methylene-2,5-heptadiene (CAS Reg. No.927-O₂-6), 1-methyl-4-(1-methylethylidene)-cyclohexene (CAS Reg. No.586-62-9), 3,7,11-trimethyl-(3E or 3Z, 6E or 6Z)-1,3,6,10-dodecatetraene(CAS Reg. No. 502-61-4),4-(1,5-dimethyl-4-hexenylidene)-1-methyl-cyclohexene (CAS Reg. No.495-62-5), isoprene, myrcene, dihydromyrene, linalool, terpinenes (α, β,and γ), limonene, terpinolene, menthadiene (p-3,8 or p-2,4), geraniol,nerol, geranylacetate, neryl acetate, nerolidol (CAS Reg. No.7212-44-4), farnesol (CAS Reg. No. 4602-14-0), dehydronerolidol (CASReg. No. 2387-68-0), α-bisabolol, valancene, nookatene, nootkatone,dimethyl-2,4,6-octratriene, β-phellandrences (CAS Reg. No. 6153-17-9),piperitols (−, cis and +, trans) (CAS Reg. Nos. 65733-28-0, 65733-2-9),1-methyl-1,4-cyclohexadiene, methyl cyclopentadiene dimer, ethylidenenorbornene, dipentene, carvestrene, carvone (− or +), alloocimenes[4-trans-6-cis (CAS Reg. No. 7216-56-0) and 4-trans-6-trans (CAS Reg.No. 3016-19-1)], alloocimenols (CAS Reg. No. 18479-54-4), ionomers (CASReg. Nos. 127-41-3, 14901-07-6), guaiazulene, lanosterol (CAS Reg. No.76-63-0), squalene (CAS Reg. No. 111-O₂-4), lycopene (CAS Reg. No.502-65-8), and carotenes [β and γ (CAS Reg. Nos. 7235-40-7, 472-94-5)].

Of course, combinations of these compounds, with or without conventionalepoxy compounds, may be used, provided that excluded as the solecomponent from these compounds are those within the teachings of U.S.Pat. No. 5,948,922 (Ober) and U.S. Pat. No. 5,973,033 (Ober). That is,excluded as the sole component from these compounds are epoxy compoundswithin the following formula:

where each R is independently selected from hydrogen, methyl, ethyl,propyl, isopropyl, butyl, isobutyl, tert-butyl, C₁₋₄ alkoxy, halogen,cyano and nitro, R₁ and R₂ are each independently selected fromhydrogen, methyl, ethyl and propyl, provided that both R₁ and R₂ cannotbe hydrogen, R₃ is independently selected from hydrogen, methyl, ethyl,propyl, and isopropyl, provided at least one of R_(3a) and R_(3b), andat least one of R_(3c) and R_(3d) is independently selected from methyl,ethyl, propyl, and isopropyl, and m is 0 or 1.

Particularly desirable epoxy or oxirane compounds within formula Iinclude limonene diepoxide and gamma-terpinene diepoxide. Limonenediepoxide may be obtained commercially from Daicel Chem. Co., Ltd.,Japan under the tradename “CELLOXIDE” 3000.

Other particularly desirable epoxy or oxirane compounds include methylcyclopentadiene diepoxide dimer (“MCPD dimer”), ethylidene norbornenediepoxide (“ENB diepoxide”), and nopol epoxide glycidyl ether (“NEGE”).

The presence in the curable resin component of one or more epoxycompounds having at least one oxirane or thiirane linkage substituted onat least three of the substitutable positions on the oxirane or thiiranecarbons, respectfully, with an alkyl, alkenyl or aryl substituent havinga carbon content of one to about twelve carbon atoms, with or withoutsubstitution or interuption by one or more heteroatoms or halogensallows for repair, replacement, recovery and/or recycling of operativeelectronic components from assemblies that have become at least in partinoperative.

The compounds with the oxirane linkage(s) can be prepared fromolefinically unsaturated compounds, many of which having at least twoolefinic linkages, with at least one of the olefinic linkages beingsubstituted on at least three of the substitutable positions on theepoxy carbons with an alkyl, alkenyl or aryl substituent having a carboncontent of 1 to about twelve carbon atoms, with or without substitutionor interuption by one or more heteroatoms or halogens. This olefinicallyunsaturated compound may then be contacted with an epoxidation agent inan amount and under conditions appropriate to react with the olefiniclinkages to form an inventive compound having an oxirane linkage.

Appropriate epoxidation agents useful in forming oxirane rings includeperacids (such as peracetic acid, perbenzoic acid, meta-chloroperbenzoicacid, tungstic acid/hydrogen peroxide [see U.S. Pat. No. 4,562,276(Venturello) and U.S. Pat. No. 5,274,140 (Venturello) and the like],with the reaction carried out until epoxidization of the olefin linkagesis at least substantially complete, typically within a period of time offrom 2 to 18 hours.

As regards preparation of inventive compounds having at least onethiirane linkage, conventional synthetic methods may be used, such asthose described in U.S. Pat. No. 3,378,522 (Martin), the disclosure ofwhich is hereby expressly incorporated herein by reference.

To that end, particularly desirable episulfide or thiirane compoundswithin formula I include the episulfides or thiiranes of limonene,gamma-terpinene, methyl cyclopentadiene dimer, ethylidene norbornene,and nopol glycidyl ether.

As an inorganic filler component, many materials are potentially useful.For instance, the inorganic filler component may often includereinforcing silicas, such as fused silicas, and may be untreated ortreated so as to alter the chemical nature of their surface. Virtuallyany reinforcing fused silica may be used.

Particularly desirable ones have a low ion concentration and arerelatively small in particle size (e.g., in the range of about 2-10microns, such as on the order of about 2 microns), such as the silicacommercially available from Admatechs, Japan under the trade designationSO-E5.

Other desirable materials for use as the inorganic filler componentinclude those constructed of or containing aluminum oxide, siliconnitride, aluminum nitride, silica-coated aluminum nitride, boron nitrideand combinations thereof.

The inorganic filler component may be present in the inventivecomposition in an amount up to 70 weight percent, such as in the rangeof about 5 to about 60 weight percent, particularly about 10 to about 50weight percent, more particularly about 15 to about 40 weight percent,and even more particularly about 20 to about 35 weight percent, such asabout 30 weight percent.

The curing agent component should include materials capable ofcatalyzing the polymerization of the epoxy resin component of theinventive compositions. Desirable curing agents for use with the presentinvention include an anhydride component, a nitrogen-containingcomponent, such as an amine compound, an amide compound, and animidazole compound, or combinations thereof.

Appropriate anhydride compounds for use herein include mono- andpoly-anhydrides, such as hexahydrophthalic anhydride (“HHPA”) and methylhexahydrophthalic anhydride (“MHHPA”) (commercially available fromLindau Chemicals, Inc., Columbia, S.C., used individually or as acombination, which combination is available under the trade designation“LINDRIDE” 62C) and5-(2,5-dioxotetrahydrol)-3-methyl-3-cyclohexene-1,2-dicarboxylicanhydride (commercially available from ChrisKev Co., Leewood, Kans.under the trade designation B-4400).

Of course, combinations of these anhydride compounds are also desirablefor use in the compositions of the present invention.

The nitrogen-containing compound includes amine compounds such aspolyamines and di- and tri-aza compounds, modified amine compounds,amide compounds, imidazole compounds, and combinations thereof.

Examples of the amine compounds include the following alkyl poly amines:diethylenetriamine, triethylenetetraamine, diethylaminopropylamine, andquinoxaline.

Examples of the di- or tri-aza compounds include:

-   1,5-diazabicyclo[4.3.0]non-5-ene-   1,8-diazabicyclo[5.4.0]undec-7-ene (“DBU”);-   1,5,7-triazabicyclo[4.4.0]dec-5-ene; and    the bicyclo mono- and di-aza compounds:-   quinuclidine; and-   1,4-diazabicyclo[2.2.2.]octane.

Examples of modified amine compounds include epoxy amine additivesformed by the addition of an amine compound to an epoxy compound.

Of course, combinations of these amine compounds are also desirable foruse in the compositions of the present invention.

Examples of amide compounds include cyano-functionalized amides, such asdicyandiamide.

The imidazole compounds may be chosen from imidazole, isoimidazole, andsubstituted imidazoles—such as alkyl-substituted imidazoles (e.g.,2-methyl imidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole,butylimidazole, 2-heptadecenyl-4-methylimidazole, 2-undecenylimidazole,1-vinyl-2-methylimidazole, 2-n-heptadecylimidazole, 2-undecylimidazole,2-heptadecylimidazole, 1-benzyl-2-methylimidazole,1-propyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole,1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole,1-cyanoethyl-2-phenylimidazole, 1-guanaminoethyl-2-methylimidazole andaddition products of an imidazole and trimellitic acid,2-n-heptadecyl-4-methylimidazole and the like, generally where eachalkyl substituent contains up to about 17 carbon atoms and desirably upto about 6 carbon atoms), and aryl-substituted imidazoles [e.g.,phenylimidazole, benzylimidazole, 2-methyl-4,5-diphenylimidazole,2,3,5-triphenylimidazole, 2-styrylimidazole, 1-(dodecylbenzyl)-2-methylimidazole,2-(2-hydroxyl-4-t-butylphenyl)-4,5-diphenylimidazole,2-(2-methoxyphenyl)-4,5-diphenylimidazole,2-(3-hydroxyphenyl)-4,5-diphenylimidazole,2-(p-dimethylaminophenyl)-4,5-diphenylimidazole,2-(2-hydroxyphenyl)-4,5-diphenylimidazole,di(4,5-diphenyl-2-imidazole)-benzene-1,4,2-naphthyl-4,5-diphenylimidazole, 1-benzyl-2-methylimidazole,2-p-methoxystyrylimidazole, and the like, generally where each arylsubstituent contains up to about 10 carbon atoms and desirably up toabout 8 carbon atoms].

Examples of commercial imidazole compounds are available from AirProducts, Allentown, Pa. under the trade designation “CUREZOL” 1B2MZ andfrom Synthron, Inc., Morganton, N.C. under the trade designation“ACTIRON” NXJ-60.

Examples of the modified imidazole compounds include imidazole adductsformed by the addition of an imidazole compound to an epoxy compound.For instance, “AJICURE” PN-23, commercially available from AjinomotoCo., Inc., Tokyo, Japan, is believed to be an adduct of EPON 828(bisphenol-A-type epoxy resin, epoxy equivalent 184-194, commerciallyavailable from Shell Chemical Co.), 2-ethyl-4-methylimidazole andphthalic anhydride. Others commercially available ones from Ajinomotoinclude “AMICURE” MY-24, “AMICURE” GG-216 and “AMICURE” ATU CARBAMATE.In addition, “NOVACURE” HX-3722 (an imidazole/bisphenol A epoxy adductdispersed in bisphenol A epoxy) and “NOVACURE” HX-3921 HP, commerciallyavailable from Asahi-Ciba, Ltd., may also be used.

Of course, combinations of these imidazole compounds are also desirablefor use in the compositions of the present invention.

The curing agent component may be used in an amount of from about 1 toabout 100 weight percent, such as about 3 to about 50 weight percent,based on the weight of the curable resin component, depending of courseon the type and identity of the curing agent component.

In addition, the composition may also include a flowability agent, suchas a silane and/or titanate.

Appropriate silanes for use herein include octyl trimethoxy silane(commercially available from OSI Specialties Co., Danbury, Conn. underthe trade designation A-137), and methacryloxy propyl trimethoxy silane(commercially available from OSI under the trade designation A-174).

Appropriate titanates for use herein include titanium IV tetrakis[2,2-bis[(2-propenyloxy)methyl]-1-butanolato-0][bis(ditridecylphosphito-0), dihydrogen]₂ (commercially available fromKenrich Petrochemical Inc., Bayonne, N.J. under the trade designationKR-55).

When used, the flowability agent may be used in an amount up to about 5weight percent, such as about 0.05 weight percent to about 2 weightpercent, desirably about 0.1 to about 1 weight percent, based on thetotal weight of the composition.

In addition, adhesion promoters, such as the silanes, glycidyltrimethoxysilane (commercially available from OSI under the tradedesignation A-187) or gamma-amino propyl triethoxysilane (commerciallyavailable from OSI under the trade designation A-1100), may be used.

When used, the adhesion promoters may be used in an amount of about 1 toabout 20 weight percent, such as about 5 to about 15 weight percent,desirably about 8 to about 12 weight percent, based on the total weightof the composition.

Cyanate esters may also be used in the inventive compositions. Thecyanate esters useful as a component in the inventive compositions maybe chosen from dicyanatobenzenes, tricyanatobenzenes,dicyanatonaphthalenes, tricyanatonaphthalenes, dicyanato-biphenyl,bis(cyanatophenyl)methanes and alkyl derivatives thereof,bis(dihalocyanatophenyl)propanes, bis(cyanatophenyl)ethers,bis(cyanatophenyl)sulfides, bis(cyanatophenyl)propanes,tris(cyanatophenyl)phosphites, tris(cyanatophenyl)phosphates,bis(halocyanatophenyl)methanes, cyanated novolac,bis[cyanatophenyl(methylethylidene)]benzene, cyanatedbisphenol-terminated thermoplastic oligomers, and combinations thereof.

More specifically, aryl compounds having at least one cyanate estergroup on each molecule and may be generally represented by the formulaAr(OCN)_(m), where Ar is an aromatic radical and m is an integer from 2to 5. The aromatic radical Ar should contain at least 6 carbon atoms,and may be derived, for example, from aromatic hydrocarbons, such asbenzene, biphenyl, naphthalene, anthracene, pyrene or the like. Thearomatic radical Ar may also be derived from a polynuclear aromatichydrocarbon in which at least two aromatic rings are attached to eachother through a bridging group. Also included are aromatic radicalsderived from novolac-type phenolic resins—i.e., cyanate esters of thesephenolic resins. The aromatic radical Ar may also contain furtherring-attached, non-reactive substituents.

Examples of such cyanate esters include, for instance,1,3-dicyanatobenzene; 1,4-dicyanatobenzene; 1,3,5-tricyanatobenzene;1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene;1,3,6-tricyanatonaphthalene; 4,4′-dicyanato-biphenyl;bis(4-cyanatophenyl)methane and 3,3′,5,5′-tetramethylbis(4-cyanatophenyl)methane;2,2-bis(3,5-dichloro-4-cyanatophenyl)propane;2,2-bis(3,5-dibromo-4-dicyanatophenyl)propane;bis(4-cyanatophenyl)ether; bis(4-cyanatophenyl)sulfide;2,2-bis(4-cyanatophenyl)propane; tris(4-cyanatophenyl)-phosphite;tris(4-cyanatophenyl)phosphate; bis(3-chloro-4-cyanatophenyl)methane;cyanated novolac; 1,3-bis[4-cyanatophenyl-1-(methylethylidene)]benzeneand cyanated bisphenol-terminated polycarbonate or other thermoplasticoligomer.

Other cyanate esters include cyanates disclosed in U.S. Pat. Nos.4,477,629 and 4,528,366, the disclosure of each of which is herebyexpressly incorporated herein by reference; the cyanate esters disclosedin U.K. Pat. No. 1,305,702, and the cyanate esters disclosed inInternational Patent Publication WO 85/02184, the disclosure of each ofwhich is hereby expressly incorporated herein by reference. Of course,combinations of these cyanate esters within the imidazole component ofthe compositions of the present invention are also desirably employedherein.

A particularly desirable cyanate ester for use herein is availablecommercially from Ciba Specialty Chemicals, Tarrytown, N.Y. under thetradename “AROCY” L10 [1,1-di(4-cyanatophenylethane)].

When used, the cyanate esters may be used in an amount of about 1 toabout 20 weight percent, such as about 5 to about 15 weight percent,desirably about 8 to about 12 weight percent, based on the total weightof the epoxy resin component.

Conventional additives may also be used in the compositions of thepresent invention to achieve certain desired physical properties of thecomposition, the cured reaction product, or both.

For instance, it may be desirable in certain instances (particularlywhere a large volume of inorganic filler component is used) to include areactive co-monomer component for the curable resin component, such as areactive diluent.

Appropriate reactive diluents for use herein may include monofunctionalor certain multifunctional epoxy resins and episulfides. The reactivediluent should have a viscosity which is lower than that of the curableresin component. Ordinarily, the reactive diluent should have aviscosity less than about 250 cps. In the event such a monofunctionalepoxy resin is included as a reactive diluent, such resin should beemployed in an amount of up to about 50 weight percent, based on weightof the curable resin component.

The monofunctional epoxy resin should have an epoxy group with an alkylgroup of about 6 to about 28 carbon atoms, examples of which includeC₆₋₂₈ alkyl glycidyl ethers, C₆₋₂₈ fatty acid glycidyl esters and C₆₋₂₈alkylphenol glycidyl ethers.

Commercially available monofunctional epoxy resin reactive diluentsinclude those from Pacific Epoxy Polymers, Richmond, Mich., under thetrade designations PEP-6770 (glycidyl ester of neodecandoic acid),PEP-6740 (phenyl glycidyl ether) and PEP-6741 (butyl glycidyl ether).

Commercially available multifunctional epoxy resin reactive diluentsinclude those from Pacific Epoxy Polymers, under the trade designationsPEP-6752 (trimethylolpropane triglycidyl ether) and PEP-6760 (diglycidylaniline).

The compositions of the present invention may further include otheradditives, such as defoaming agents, leveling agents, dyes, andpigments. Moreover, photopolymerization initiators may also beincorporated therein, provided that such initiators do not adverselyaffect the properties of the composition or reaction products formedtherefrom.

The present invention also includes novel diepoxide-containingcompounds, set forth in detail below.

where R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are individually selected from thegroup consisting of hydrogen, alkyl from one to eight carbon atoms,alkenyl from two to eight carbon atoms and combinations thereof, and Xand X¹ are individually selected from O and S.

More specific examples of such novel diepoxide-containing compoundsinclude:

The thermosetting resin compositions of the present invention may be ofthe one-pack type, in which all the ingredients are mixed together, orof the two-pack type in which the curable component(s), is (are)included in one part and the curing agent is stored separately in asecond part, and mixed together only prior to use.

During application, the thermosetting resin compositions according tothe present invention penetrate and flow readily into the space betweenthe semiconductor chip and the circuit board, or at least show areduction in viscosity under heated or use conditions thus penetratingand flowing easily.

Generally, it is desirable to prepare thermosetting resin compositionsof this invention by selecting the types and proportions of variouscomponents to reach a viscosity at a temperature of 25° C. in the rangeof 500 to 70,000 cps, such as 800 to 20,000 cps, depending on the amountpresent (if any) of an inorganic filler component, so as to improve itsability to penetrate into the space (e.g., of 10 to 500 μm) between thecircuit board and the semiconductor device. At this viscosity, the geltimes of the compositions will also be tailored to a specified period oftime (such as 15 seconds, or 1 or 2 minutes) at a temperature of about150° C. In such case, the inventive compositions should show no orsubstantially no increase of viscosity after a period of time of aboutsix hours. With such a gel time, the compositions penetrate into thespace (e.g., of 10 to 500 μm) between the circuit board and thesemiconductor device relatively rapidly, and allow for a greater numberof assemblies to be filled without observing a viscosity increase in thecomposition thereby rendering it less effective for application.

Reference to FIG. 1 shows a mounted structure (i.e., a FC package) inwhich a thermosetting resin composition of the present invention hasbeen applied and cured.

The FC package 4 is formed by connecting a semiconductor chip (a barechip) 2 to a carrier substrate 1 (e.g., a circuit board) and sealing thespace therebetween suitably with a thermosetting resin composition 3.

More specifically, for example, in the assembly of FC semiconductordevices using SBB technology, the semiconductor chip 2 may be passedover a substrate bearing a conductive adhesive paste (such as ametal-filled epoxy) to form a layer thereof on the semiconductor chip 2.The layer is ordinarily formed by a printing mechanism. The conductiveadhesive paste may be applied on either the carrier substrate or thesemiconductor chip. One way to do this is with the stencil claimed anddescribed in International Patent Publication No. PCT/FR95/00898.Alternatively, this connection may also be made by an anisotropicallyconductive adhesive. See International Patent Publication No.PCT/US97/13677.

Thereafter, the semiconductor chip 2 is positioned over the carriersubstrate 1 in such a manner so that the semiconductor chip 2 is inalignment with the electrodes 5 and 6 on the carrier substrate 1, nowcoated with a patterned layer of conductive adhesive paste or solder, 7and 8. The conductive adhesive paste may be cured by a variety of ways,though ordinarily a heat cure mechanism is employed.

In order to improve reliability, the space between the semiconductorchip 2 and the carrier substrate 1 is sealed with a thermosetting resincomposition 3. The cured product of the thermosetting resin compositionshould completely fill that space.

The semiconductor chip ordinarily may be coated with a polyimide-,poly-benzocyclobutane- or silicone nitride-based material to passivateenvironmental corrosion.

Carrier substrates may be constructed from ceramic substrates of Al₂O₃,SiN₃ and mullite (Al₂O₃—SiO₂); substrates or tapes of heat-resistantresins, such as polyimides; glass-reinforced epoxy; ABS and phenolicsubstrates which are also used commonly as circuit boards; and the like.Any electrical connection of the semiconductor chip to the carriersubstrate may be used, such as connection by a high-melting solder orelectrically (or anisotropically) conductive adhesive and the like. Inorder to facilitate connections, particularly in SBB technology, theelectrodes may be formed as wire bond bumps.

After the semiconductor chip is electrically connected to the carriersubstrate, the resulting structure is ordinarily subjected to acontinuity test or the like. After passing such test, the semiconductorchip may be fixed thereto with a thermosetting resin composition, asdescribed below. In this way, in the event of a failure, thesemiconductor chip may be removed before it is fixed to the carriersubstrate with the thermosetting resin composition.

Using a suitable application means, such as a dispenser, a thermosettingresin composition in accordance with this invention is applied to theperiphery of the electronically-connected semiconductor chip. Thecomposition penetrates by capillary action into the space between thecarrier substrate and the semiconductor chip.

The thermosetting resin composition is then thermally cured by theapplication of heat. During the early stage of this heating, thethermosetting resin composition shows a significant reduction inviscosity and hence an increase in fluidity, so that it more easilypenetrates into the space between the carrier substrate and thesemiconductor chip. Moreover, by preheating the carrier substrate, thethermosetting resin composition is allowed to penetrate fully into theentire space between the carrier substrate and the semiconductor chip.

Thermosetting resin compositions of the present invention may ordinarilybe cured by heating to a temperature in the range of about 120 to about180° C. for a period of time of about 0.5 to 30 minutes. However,generally after application of the composition, an initial cure time ofabout 1 minute sets up the composition, and complete cure is observedafter about 5 to about 15 minutes at a temperature of about 165° C.Thus, the composition of the present invention can be used at relativelymoderate temperatures and short-time curing conditions, and henceachieve very good productivity.

The amount of thermosetting resin composition applied should be suitablyadjusted so as to fill almost completely the space between the carriersubstrate and the semiconductor chip, which amount of course may varydepending on application.

Cured reaction products of the thermosetting resin compositions of thepresent invention demonstrate excellent adhesive force, heat resistanceand electric properties, and acceptable mechanical properties, such asflex-cracking resistance, chemical resistance, moisture resistance andthe like, for the applications for which they are used herein.

In the mounting process by using the thermosetting resin composition ofthe present invention, after the semiconductor device is mounted on thecircuit board as described above, the resulting structure is tested withrespect to characteristics of the semiconductor device, connectionbetween the semiconductor device and the circuit board, other electricalcharacteristics, and the state of sealing. In the event a failure isfound, repair can be made in the following manner and as shown in theflow diagram depicted in FIG. 2.

The area around the semiconductor device which has failed is heated at atemperature of about 190 to about 260° C. for a period of time rangingfrom about 10 seconds to about 2 minutes. (See FIG. 2, step 1.)Desirably, the temperature should be maintained in the range of about210 to about 220° C. and the period of time should be within the 30seconds to 2 minute range. Localized heating is particularly desirable,such as the application of hot air to the failure site by a heating gun.

As soon as the solder is melted and the resin is softened by partialdecomposition to cause a reduction in bond strength, the semiconductordevice may be pulled apart and removed from the substrate, such as withtweezers or pliers, or through automated processes.

After the semiconductor device 4 is removed, a residue of the curedreaction product of the thermosetting resin composition and a residue ofthe solder are left on the circuit board 5. The residue of the curedproduct of the thermosetting resin composition can be removed, forexample, by scraping it off after the residue has been softened byheating it to a predetermined temperature. The residue of the solder canbe removed, for example, by use of a solder-absorbing braided wire. (SeeFIG. 2, step 2.) Alternatively, use of a dremel at about 25,000 rpm ormore, followed by application of a flat-end horse hair brush, willachieve the desired result.

Finally, a new semiconductor chip may be mounted azain onto the circuitboard (which has been cleaned, with fluxing, as described above) in themanner as described above. (See FIG. 2, step 3.) Following mounting, athermosetting resin composition in accordance with this invention may bedispensed in the area between the semiconductor device and the circuitboard, and cured. (See FIG. 2, step 4.) Repair of the failure site isthus completed.

Where a failure site is found in the circuit board, the semiconductordevice can be reused by removing the residue of the cured reactionproduct of the thermosetting resin composition and the residue of thesolder left on the bottom of the semiconductor device in the same manneras described above.

The present invention will be more readily appreciated with reference tothe examples which follow.

EXAMPLES Synthesis of Epoxides

Limonene [125 grams (477 mmoles)] and methylene chloride (1000 ml) wereadded to a reaction flask, and the resulting solution cooled with an icebath to a temperature in the range of about 0 to about 10° C. Then, 70%m-chloroperbenzoic acid [259.5 grams (1050 mmoles)] was added withstirring in small increments over a period of time of about 110 minutes,while maintaining the temperature of the reaction mixture below about15° C. The reaction mixture was stirred overnight, while maintaining thetemperature below about 15° C. m-Chlorobenzoic acid was formed as aprecipitate, and filtered off, with the organic filtrate washed twicewith 500 ml portions of 10% aqueous Na₂SO₃, twice with 500 ml portionsof saturated aqueous Na₂CO₃ solution, and twice with 500 ml portions ofwater. The organic layer was separated, dried over anhydrous MgSO₄, andthen filtered. Basic alumina (50 grams) was then added to the organicfiltrate, with the mixture stirred for a period of time of about 45minutes, and then filtered. The organic solvent was removed underreduced pressure, and the resulting product vacuum distilled. Limonenediepoxide was obtained in an amount of 120.7 grams (86% yield). ¹H NMR(CDCl₃) δ 3.0 (m, 1, C

C—H), 2.5 (m, 2, C

C—H), 1.0-2.2 (m, 7, CH, CH₂), 1.3 (s, 3, ring CH₃), 1.2 (m, 3,side-chain CH₃); IR (neat) 2932, 1436, 1381, 853, 763 cm⁻¹.

Gamma-terpinene diepoxide, methyl cyclopentadiene dimer diepoxide andethylidene norbornene diepoxide were prepared in the same manner. Theirspectral data are given as follows: ¹H NMR (CDCl₃) δ 2.5-3.0 (m, 2, C

C—H), 2.1 (m, 4, CH₂), 1.6 (m, 1, CH), 1.3 (s, 3, CH₃), 1.0 (m, 6,side-chain CH₃); IR (neat) 2963, 1467, 1107, 834, 709 cm⁻¹; ¹H NMR(CDCl₃) δ 3.0-3.5 (m, 1, C

C—H), 2.5-2.7 (m, 1.5, C

C—H), 1.2-1.9 (m, 8, CH, CH₂), 1.4-1.5 (m, 6, CH₃); IR (neat) 2956,1448, 1078, 829, 759 cm⁻¹; and ¹H NMR (CDCl₃) δ 3.0-3.5 (m, 2, C

C—H), δ 3.0-3.5 (br s, 1, C

C—H), 1.1-2.3 (m, 6, CH, CH₂), 1.3 (d, 3, CH₃); IR (neat) 2979, 1449,1376, 1008, 852, 757 cm⁻¹, respectively.

The yields and boiling points of these diene diepoxides are given belowin Table 1. TABLE 1 Yields and Boiling Points of Certain DieneDiepoxides Physical Limonene γ-Terpinene MCPD Dimer ENB PropertiesDiepoxide Diepoxide Diepoxide Diepoxide Distillation 68-70 — 90-10065-67 Temperature (° C.) Distillation 850 — 780 850 Pressure (mTorr)Crude 89 Quantitative 93.7 96.2 Yield (%) Distilled 61 — 75.3 71.8 Yield(%) Physical Clear Opaque liquid Friable solid Clear liquid Appearanceliquid GC 98.3 — 96.3 99.3 (% Purity)

Nopol epoxide glycidyl ether was prepared as follows:

To a four-necked 1000 ml reaction flask, equipped with a mechanicalstirrer, thermometer, and condenser, was added 200 ml of 50 weightpercent aq. NaOH, epibromohydrin (144.3 g, 1.03 mol), andtetrabutylammonium hydrogen sulfate (4.2 g, 12 mmol). The mixture wasstirred vigorously at room temperature for a period of time of about 20minutes to a pale yellow color. The mixture was then cooled to atemperature of about 10° C. in an ice/water bath. To the mixture wasadded (1R)-(−)-nopol (50 g, 295 mmol) dropwise over a period of time ofabout 30 minutes. The reaction temperature was maintained at or nearabout 10° C. during the addition. The ice/water bath was removed, andthe mixture was allowed to warm to ambient temperature, while it stirredovernight. The reaction mixture was then quenched with 500 ml of icecold water, which was added over a period of time of about 15 minutes,with stirring for an additional period of time of about 20 minutes. Themixture was transferred to a 2 liter separatory funnel, where it wastwice extracted with 200 ml of diethyl ether. The organic portion wasthen washed twice with 200 ml of sat. aq. NaCl, separated, dried overanhydrous MgSO₄, and then filtered. After filtration, the solvent wasremoved under reduced pressure. The crude product was vacuum distilledto yield about 48.1 g (74%) yield of nopol glycidyl ether, with aboiling point of about 94-96° C. at atmospheric pressure. The spectraldata are given as follows: ¹H NMR (CDCl₃) δ 5.25 (br s, 1, ═CH), 2.8-3.7(m, 7, OCH, OCH₂), 2.0-2.4 (m, 6, CH, CH₂), 1.6 (s, 1, CH), 1.3 (s, 3,CH₃), 1.1 (d, 1, CH), 0.8 (s, 3, CH₃) (see FIG. 15); FT-IR 2927, 2908,1468, 1364, 1108, 910, 849 cm⁻¹ (see FIG. 16).

To a four-necked 500 ml flask equipped with a mechanical stirrer,thermometer, and condenser, was added nopol glycidyl ether (48.2 g,205.4 mmol), and methylene chloride (250 ml). To the solution was added70% m-chloroperoxybenzoic acid (53 g, 215 mmol) over a period of time ofabout 2 hours. The reaction temperature was maintained below about 15°C. with an ice/water bath during the addition. After the addition wascomplete, the reaction mixture was stirred overnight and maintained at atemperature below about 20° C. with an ice water bath. m-Chlorobenzoicacid was formed as a precipitate, and filtered the organic filtratewashed off, twice with 200 ml portions of 10% aq. Na₂SO₃, twice with 200ml portions sat. aq. NaHCO₃, and twice with 200 ml portions of water.The organic layer was separated, dried over anhydrous MgSO₄, andfiltered. Solvent was removed under reduced pressure, and the crudeproduct was vacuum distilled. Nopol epoxide glycidyl ether was obtainedin a yield of about 46.5 g (91%), with a boiling point of about 110-113°C. at 800 mTorr. ¹H NMR (CDCl₃) δ 2.8-3.7 (m, 8, OCH, OCH₂), 2.0-2.4 (m,8, CH, CH₂), 1.3 (s, 3, CH₃) (see FIG. 17), 0.9 (s, 3, CH₃); FT-IR 2917,1470, 1110, 911, 855, 761 cm⁻¹ (see FIG. 18).

Thermosetting Resin Compositions

Preparation

A thermosetting resin composition (Sample No. 1) was prepared by mixingtogether for a period of time of about 10 minutes at room temperature inan open vessel the following components:

-   -   1. an epoxy resin component including        -   51.7 weight percent of limonene diepoxide prepared as above,            and    -   2. a curing agent component including        -   46.5 weight percent of MHHPA,        -   0.8 weight percent of benzyldimethyl amine, and        -   1 weight percent of ethylene glycol.

Four additional compositions (Samples Nos. 2-5) were prepared in thismanner, substituting for the limonene diepoxide, the same amounts ofgamma-terpinene diepoxide, Compound XVI of the '922 patent, and thecommercially available epoxy resins, ERL-4221 and RE-404-S. [See Table2(a).]

A further thermosetting resin composition (Sample No. 6) was prepared asdescribed above by mixing together the following components:

-   -   1. an epoxy resin component including        -   51.7 weight percent of limonene diepoxide, and    -   2. a curing agent component including        -   4.7 weight percent of dicyandiamide, and        -   1.9 weight percent of an imidazole            -   (commercially available from Synthron, Inc. under the                trade designation “ACTIRON” NXJ-60).

Four additional compositions (Samples Nos. 7-10) were prepared as SampleNo. 6, substituting for the limonene diepoxide, the same amounts ofgamma-terpinene diepoxide, Compound XVI of the '922 patent, and thecommercially available epoxy resins ERL-4221 and RE-404-S. [See Table2(a).] TABLE 2(a) Component Sample No./Amount (weight percent) TypeIdentity 1 2 3 4 5 6 7 8 9 10 Epoxy Limonene 51.7 — — — — 93.4 — — — —Resin Diepoxide Terpinene — 51.7 — — — — 93.4 — — — Diepoxide ERL-4221 —— — 51.7 — — — — 93.4 — Compound XVI — — 51.7 — — — — 93.4 — — RE-404-S— — — — 51.7 — — — — 93.4 Curing NXJ-60 — — — — — 1.9 1.9 1.9 1.9 1.9Agent (Imidazole) 1B2MZ — — — — — — — — — — (Imidazole) CG-1400 — — — —— 4.7 4.7 4.7 4.7 4.7 (Dicyandiamide) MHHPA 46.5 46.5 46.5 46.5 46.5 — —— — — (Anhydride) Benzyldimethyl 0.8 0.8 0.8 0.8 0.8 — — — — — amineEthylene glycol 1 1 1 1 1 — — — — —

A further thermosetting resin composition (Sample No. 11) was preparedwith a limonene diepoxide/RE-404-S combination, designed with animidazole/dicyandiamide cure, as described above by mixing together thefollowing components:

-   -   1. an epoxy resin component including        -   74.7 weight percent of limonene diepoxide, and        -   18.7 weight percent of RE-404-S, and    -   2. a curing agent component including        -   4.7 weight percent of dicyandiamide, and        -   1.9 weight percent of the imidazole, NXJ-60.

Two additional compositions (Samples Nos. 12-13) were prepared as SampleNo. 11, except that the weight percent of the limonene diepoxide wasdecreased and the weight percent of the RE-404-S was increased. [SeeTable 2(b).]

A still further thermosetting resin composition (Sample No. 14) wasprepared with a terpinene diepoxide/RE-404-S combination, designed withan imidazole/dicyandiamide cure, as described above by mixing togetherthe following components:

-   -   1. an epoxy resin component including        -   74.7 weight percent of terpinene diepoxide, and        -   18.7 weight percent of RE-404-S, and    -   2. a curing agent component including        -   4.7 weight percent of dicyandiamide, and        -   1.9 weight percent of the imidazole, NXJ-60.

Two additional compositions (Samples Nos. 15-16) were prepared as SampleNo. 14, except that the weight percent of the terpinene diepoxide wasdecreased and the weight percent of the RE-404-S was increased. [SeeTable 2(b).]

An additional thermosetting resin composition (Sample No. 17) wasprepared based on a limonene diepoxide/RE-404-S combination, designedwith an imidazole/dicyandiamide cure, as described above by mixingtogether the following components:

-   -   1. an epoxy resin component including        -   39.17 weight percent of limonene diepoxide, and        -   26.11 weight percent of RE-404-S;    -   2. a curing agent component including        -   1.4 weight percent of the imidazole, NXJ-60, and        -   3.14 weight percent of dicyandiamide;    -   3. 30 weight percent of an inorganic filler component, SO-E5        silica; and    -   4. a flowability agent including        -   the silanes, octyl (A-137, 0.06 weight percent) and glycidyl            (A-187, 0.06 weight percent), and        -   titanate (KR-55, 0.06 weight percent).

Five additional compositions (Sample Nos. 18-21 and 25) were preparedalong these lines, except that the limonene diepoxide/RE-404-S ratio wasvaried, and as to Sample Nos. 21 and 25, the weight percents of thecomponents of the flowability agent were also varied. [See Tables 2(b)and 2(c).] TABLE 2(b) Component Sample No./Amount (weight percent) TypeIdentity 11 12 13 14 15 16 17 18 19 20 Epoxy Limonene 74.7 65.4 56 — — —39.17 32.64 26.11 19.58 Resin Diepoxide Terpinene — — — 74.7 65.4 56 — —— — Diepoxide RE-404-S 18.7 28 37.4 18.7 28 37.4 26.11 32.64 39.17 45.70BEO-60E — — — — — — — — — — Inorganic SO-ES — — — — — — 30 30 30 30Filler (Silica) Curing NXJ-60 1.9 1.9 1.9 1.9 1.9 1.9 1.4 1.4 1.4 1.4Agent (Imidazole) 1B2MX — — — — — — — — — — (Imidazole) CG-1400 4.7 4.74.7 4.7 4.7 4.7 3.14 3.14 3.14 3.14 (Dicyandiamide) Flowability A-137(Silane) — — — — — — 0.06 0.06 0.06 0.06 Agent A-187 (Silane) — — — — —— 0.06 0.06 0.06 0.06 KR-55 — — — — — — 0.06 0.06 0.06 0.06 (Titanate)Pigment Red — — — — — — — — — —

A further additional thermosetting resin composition (Sample No. 22) wasprepared based on a limonene diepoxide/RE-404-S combination, designedwith an anhydride cure, as described above by mixing together thefollowing components:

-   -   1. an epoxy resin component including        -   10.83 weight percent of limonene diepoxide, and        -   16.24 weight percent of RE-404-S;    -   2. a curing agent component including        -   24.36 weight percent of LINDRIDE 62C,        -   2.71 weight percent of B-4400, and        -   0.11 weight percent of the imidazole, NXJ-60;    -   3. 45 weight percent of an inorganic filler component, SO-E5        silica;    -   4. a flowability agent including        -   the silanes (A-137, 0.09 weight percent) and (A-187, 0.12            weight percent), and        -   titanate (KR-55, 0.45 weight percent); and    -   5. 0.1 weight percent of red pigment.

Two additional compositions (Sample Nos. 23-24) were prepared alongthese lines, except that the limonene diepoxide/RE-404-S ratio wasvaried, the weight percents of the components of the anhydride cureagent were also varied, and the weight percent of the inorganic fillercomponent were varied as well. [See Table 2(c).] TABLE 2(c) ComponentSample No./Amount (weight percent) Type Identity 21 22 23 24 25 26 27 2829 30 Epoxy Limonene 26.09 10.83 12.12 8.58 19.50 40 28 24 20 12 ResinDiepoxide RE-404-S 39.14 16.24 22.52 15.92 45.50 — — — — — BEO-60E — — —— — — — — — 12 Inorganic SO-ES 30 45 30 50 30 — 30 40 50 40 Filler(Silica) Curing NXJ-60 1.4 — — — 1.39 — — — — — Agent (Imidazole) 1B2MZ— 0.11 0.14 0.098 — — — — — — (Imidazole) CG-1400 3.14 — — 3.13 — — — —— — (Dicyandiamide) LINDRIDE 62C — 24.36 34.64 20.82 — — — — — —(Anhydride) B-4400 — 2.71 — 3.68 — — — — — — (Anhydride) NOVACURE — — —— — 60 42 36 30 36 HX-3921 HP (Latent hardener) Flowability A-137(Silane) 0.06 0.09 0.06 0.10 0.06 — — — — — Agent A-187 (Silane) 0.120.12 0.12 0.20 0.12 — — — — — KR-55 (Titanate) 0.06 0.45 0.30 0.50 0.30— — — — — Pigment Red — 0.1 0.1 0.1 — — — — — —

Yet a further additional thermosetting resin composition (Sample No. 26)was prepared based on a limonene diepoxide (commercially available fromDaicel Chem. Co., Ltd., Japan under the tradename “CELLOXIDE” 3000),designed to cure with a latent hardener (commercially available fromAsahi-Ciba, Ltd., Japan under the tradename “NOVACURE” HX-3921 HP), andwithout a second epoxy resin, as described above by mixing together thefollowing components:

-   -   1. an epoxy resin component including        -   40 weight percent of limonene diepoxide; and    -   2. a curing agent component including        -   60 weight percent of “NOVACURE” HX-3921 HP.

Four additional compositions (Sample Nos. 27-30) were prepared alongthese lines, except that the limonene diepoxide/latent hardener ratiowas varied, and an inorganic filler component was included in variousweight percents, and a second epoxy resin was included in Sample No.0.30. [See Table 2(c).] TABLE 2(d) Component Sample No./Amount (weightpercent) Type Identity 31 32 33 34 35 36 37 38 39 40 Epoxy Limonene — —12.12 8.58 19.50 40 28 24 20 12 Resin Diepoxide RE-404-S — — 22.52 15.9245.50 — — — — — Ethylidene 51.7 — — — — — — — — — Norbornene DiepoxideMethyl Cyclopentadiene — 51.7 — — — — — — — — Dimer Diepoxide InorganicSO-ES — — 30 50 30 — 30 40 50 40 Filler (Silica) Curing NXJ-60 — — — —1.39 — — — — — Agent (Imidazole) 1B2MZ — — 0.14 0.098 — — — — — —(Imidazole) CG-1400 — — — 3.13 — — — — — — (Dicyandiamide) MHHPA 46.546.5 — — — — — — — — (Anhydride) LINDRIDE 62C — — 34.64 20.82 — — — — —— (Anhydride) B-4400 — — — 3.68 — — — — — — (Anhydride) NOVACURE — — — —— 60 42 36 30 36 HX-3921 HP (Latent hardener) Benzyldimethyl 0.9 0.9 — —— — — — — — amine Ethylene glycol 1 1 — — — — — — — — Flowability A-137(Silane) — — 0.06 0.10 0.06 — — — — — Agent A-187 (Silane) — — 0.12 0.200.12 — — — — — KR-55 (Titanate) 0.06 0.45 0.30 0.50 0.30 — — — — —Pigment Red — 0.1 0.1 0.1 — — — — — —

Sample Nos. 31 and 32 show thermosetting resin compositions preparedfrom ethylidene norbornene diepoxide and methyl cyclopentadiene dimerdiepoxide, respectively, designed to cure with an anhydride curingagent. Sample Nos. 33-35 show thermosetting resin compositions, based onlimonene diepoxide/RE-404-S in combination at various ratios (likeSample Nos. 21-25) designed to cure with an anhydride curing agent, animidizole curing agent, or both. Sample Nos. 36-40 show thermosettingresin compositions based on limonene diepoxide designed to cure with alatent hardener (commercially available for Asahi-Ciba, Ltd., Japanunder the tradename “NOVACURE” HX03921 HP), with and without aninorganic filler. [See Table 2(d).]

Yet a further additional thermosetting resin composition (Sample No. 41)was prepared based on a limonene diepoxide (commercially available fromDaicel Chem. Co., Ltd., Japan under the tradename “CELLOXIDE” 3000),designed to cure with a latent hardener (commercially available fromAsahi-Ciba, Ltd., Japan under the tradename “NOVACURE” HX-3921 HP),without a second epoxy resin, as described above by mixing together thefollowing components:

-   -   1. an epoxy resin component including        -   40 weight percent of limonene diepoxide; and    -   2. a curing agent component including        -   60 weight percent of “NOVACURE” HX-3921 HP.

Nine additional compositions (Sample Nos. 42-49) were prepared alongthese lines, except that the type and amount of the epoxy resin wasvaried as noted, and an inorganic filler component was included invarious weight percents, and a second epoxy resin was included in SampleNos. 43 and 46-49, with a third epoxy resin being including in SampleNos. 47 and 48. [See Table 2(e).] TABLE 2(e) Component Sample No./Amount(weight percent) Type Identity 41 42 43 44 45 46 47 48 49 Epoxy Limonene— — — — — — 2.79 2.76 — Resin Diepoxide Nopol Diepoxide — — — — — 26.1119.55 19.33 11.81 RE-404-S — 39.17 21.60 39.17 21.60 39.17 33.52 33.1421.92 Ethylidene 51.7 — 26.11 — 11.43 — — — — Norbornene DiepoxideMethyl Cyclopentadiene — 26.11 11.64 — — — — — — Dimer DiepoxideInorganic SO-ES — 30 30 30 30 30 40 40 30 Filler (Silica) Curing NXJ-60— 1.4 — 1.4 — 1.4 1.2 1.18 — Agent (Imidazole) 1B2MZ — — 0.14 — 0.14 — —— 0.14 (Imidazole) CG-1400 — 3.14 — 3.14 — 3.14 2.69 2.66 —(Dicyandiamide) MHHPA 46.5 — — — — — — — — (Anhydride) LINDRIDE 62C — —36.09 — 36.71 — — — 35.57 (Anhydride) Benzyldimethyl 0.9 — — — — — — — —Amine Ethylene glycol 1 — — — — — — — — Flowability A-137 (Silane) —0.06 0.05 0.06 0.05 0.06 0.08 0.4 0.05 Agent A-187 (Silane) — 0.06 0.260.06 0.12 0.08 0.08 0.12 0.12 KR-55 (Titanate) 0.06 0.06 0.30 0.06 0.250.06 0.8 0.4 0.27 Pigment Red — 0.1 0.1 0.1 0.1 0.1 — — —

In Table 2(f) below, combinations of RE-404-S together with eithermethyl cyclopentadiene dimer diepoxide, ethylidene norbornene diepoxideor nopol epoxide dylycidyl ether, at different ratios are presented asSample Nos. 50-58, designed to cure with anhydride curing agents, andSample No. 59, which is nopol epoxy glycidyl ether cured with ananhydride curing agent. TABLE 2(f) Component Sample No./Amount (weightpercent) Type Identity 50 51 52 53 54 55 56 57 58 59 Epoxy Limonene — —— — — — — — — — Resin Diepoxide Nopol Diepoxide — — — — — — 41.35 3120.7 51.7 RE-404-S 10.35 20.7 31 10.35 20.7 31 10.35 20.7 31 —Ethylidene — — — 41.35 31 20.7 — — — — Norbornene Diepoxide MethylCyclopentadiene 41.35 31 20.7 — — — — — — — Dimer Diepoxide InorganicSO-ES — — — — — — — — — — Filler (Silica) Curing NXJ-60 — — — — — — — —— — Agent (Imidazole) 1B2MZ — — — — — — — — — — (Imidazole) CG-1400 — —— — — — — — — — (Dicyandiamide) MHHPA 46.5 46.5 46.5 46.5 46.5 46.5 46.546.5 46.5 46.5 (Anhydride) LINDRIDE 62C — — — — — — — — — — (Anhydride)Benzyldimethyl 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Amine Ethyleneglycol 1 1 1 1 1 1 1 1 1 1 Flowability A-137 (Silane) — — — — — — — — —— Agent A-187 (Silane) — — — — — — — — — — KR-55 (Titanate) — — — — — —— — — Pigment Red — — — — — — — — —

Shelf-Stability

While the compositions were used upon formation (see below), they may bestored for a period of time of up to about 3 to about 6 months at atemperature of about −40° C. without experiencing viscosity increase.

After formation, the composition was transferred to a 10 ml syringe madeof non-reactive plastic.

Mounting/Underfill Process

Using cream solder (PS10R-350A-F92C; manufactured by Harima Chemicals,Inc.), a CSP having a package of 20 mm square, an electrode diameter of0.5 mm, an electrode pitch of 1.0 mm, and a carrier substrate made ofalumina was mounted on a 1.6 mm thick glass-reinforced epoxy boardhaving a circuit formed thereon.

Certain of the samples (Sample Nos. 17-25) were dispensed through a 12Gneedle connected to the syringe into the junction between the carriersubstrate and semiconductor device an assembly previously formed asabove.

After such dispensing, the assembly was transferred to an oven while thetemperature was maintained at about 165° C. The composition curedinitially after about 1 minute, and thereafter cured completely afterabout 15 minutes at that temperature.

Rather than using all the samples as underfill sealants, certain of them(Sample Nos. 1-16) were dispensed onto an aluminum dish, and cured in astep-wise manner by exposure to an elevated temperature of about 100° C.for a period of time of about 2 hours, followed by exposure to anelevated temperature of about 140° C. for a period of time of about 6hours, at the end of which time the compositions were observed to havecured.

Physical Properties

The compositions have a variety of properties in both the uncured andcured state which are measurable and useful parameters for the end userin choosing a particular formulation for a desired need.

For instance, in the uncured state, the flow rate is of interest; inreaching the cured state, the cure schedule is of interest.

The flow time allows the end user to determine the rapidity with whichthe adhesive may be applied during a fabrication process, such as acircuit assembly operation. It may be measured by passing thecomposition through a 25 μm gap between glass slides alignedperpendicular to one another, using metal shims as spacers. The timerequired for the composition to flow between the slides is then measuredat a length of about one inch, at 0.25 inch intervals. Values in secondsfor the flow times of the compositions set forth above are presented asan average of three measurements below in Table 3.

The cure schedule refers to the time required for the onset of cure tooccur at a certain temperature, in a specified period of time. This maybe seen in more detail with regard to certain of the samples prepared inaccordance with the present invention below in Table 3. TABLE 3 PhysicalProperties Flow Time Sample (secs, .5″ @ Cure Schedule No. 100° C.)(mins @ 165° C.) 17 — 10-15 18 — 10-15 19 18 10-15 20 — 10-15 21 1510-15 22 35 10-15 23 13 10-15 24 28 10-15 25 18 10-15 47 22 — 48 10 —

As the composition progresses through its cure schedule, the reactionexotherm, or enthalpy, assists in determining the effectiveness of a(co)polymerization reaction. The reaction exotherm here is measured bydifferential scanning calorimetry (“DSC”).

The peak temperature (“T_(PEAK)”) and onset temperature (“T_(ONSET)”)may be determined from the DSC measurement. These values provideinformation for minimum reasonable curing temperatures, the curingtemperature range, maximum reaction temperatures, and relative curingtime at each temperature. See Tables 4a, 4(b) and 4(c). TABLE 4(a)Physical Properties Sample Enthalpy No. (J/g) T_(PEAK) T_(ONSET) 1 266175 133 2 — — — 3  70 178 156 4  61 167 140 5 171 162 124

TABLE 4(b) Physical Properties Sample Enthalpy No. (J/g) T_(PEAK)T_(ONSET) 17 229.7 141.1 128.9 18 249.7 138.3 125.4 19 280.3 135.8 122.120 315.1 133.6 120.7 21 287.2 136.3 123.5

TABLE 4(c) Physical Properties Sample Enthalpy No. (J/g) T_(PEAK)T_(ONSET) 31 — — — 32 234 164 123 41 395 162  85 42 234 136 122 43 171171 142 44 228 135 120 45 252 166 134 46 326 153 121 49 262 168 131

In the cured state, a variety of properties are useful depending on theend use for which the composition is destined.

For instance, adhesion provides information on the strength of the bondformed by the cured reaction product, data for which is set forth inTable 5. In this adhesion evaluation, die shear adhesion is measured bya Sebastion 5 die shear measurement instrument, which measures theamount of shear strength (in Kgf) required to pull apart a die attachedto a circuit board by the cured reaction product as an underfill sealant(without a solder mask, or chipbonding adhesive). TABLE 5 Sample No./Adhesion (mg/die) (Die Shear, Kgf) 17 (3) 100 19 (3) 115 20 (3) 126 17(1-1.5) 30 19 (1-1.5) 80 20 (1-1.5) 75 42 (1-1.5) 34 44 (1-1.5) 29 46(1-1.5) 29 47 (1-1.5) 36 48 (1-1.5) 36

Reworkability determines the ease with which a cured reaction productmay be controllably degraded. The extent to which the cured reactionproduct loses mass over time at an increase in temperature may bemeasured by thermal gravimetric analysis (“TGA”), and providesinformation on the temperature (or range) at which the cured reactionproduct degrades.

Reference to FIGS. 3-4 show TGA data for cured reaction products ofSample Nos. 1-5 using an anhydride curing agent, compared with TGA datafor cured reaction products of compositions based on the commerciallyavailable epoxies ERL-4221 (Sample No. 4) and RE-404-S (Sample No. 5),and Compound XVI of the '922 and '033 patents (Sample No. 3).

Reference to FIGS. 5-6 show TGA data for cured reaction products ofSample Nos. 7-10 using an imidazole/dicyandiamide curing agent, comparedwith TGA data for cured reaction products of compositions based on thecommercially available epoxies ERL-4221 (Sample No. 9) and RE-404-S(Sample No. 10), and Compound XVI of the '922 and '033 patents (SampleNo. 8).

Reference to FIGS. 7-8 show TGA data for cured reaction products ofSample Nos. 10 and 11-16 using an imidazole/dicyandiamide curing agent,comparing TGA data for cured reaction products of compositions based onthe commercially available RE-404-S, and cured reaction products of80:20, 70:30, and 60:40 combinations of limonene diepoxide/RE-404-S(Sample Nos. 11-13) and of terpinene diepoxide (Sample Nos. 14-16).

Reference to FIGS. 9-10 show TGA data for anhydride cured reactionproducts of Sample Nos. 5 (RE-404-S), 32 (methyl cyclopentadiene dimerdiepoxide), and 50-52, having 80:20, 60:40 and 40:60 combinations ofmethyl cyclopentadiene dimer diepoxide/RE-404-S and RE-404-S, and foranhydride cured reaction products of methyl cyclopentadiene dimerdiepoxide (Sample No. 32), the commercially available epoxies ERL-4221(Sample No. 4) and RE-404-S (Sample No. 5), and Compound XVI of the '922and '033 patents (Sample No. 3).

Reference to FIGS. 11-12 show TGA data for anhydride cured reactionproducts of Sample Nos. 5, 31 (ethylidene norbornene diepoxide), 53-55,having 80:20, 60:40 and 40:60 combinations of ethylidene norbornenediepoxide/RE-404-S, and RE-404-S, and anhydride cured reaction productsof ethylidene norbornene diepoxide (Sample No. 31), the commerciallyavailable epoxies ERL-4221 (Sample No. 4) and RE-404-S (Sample No. 5),and Compound XVI of the '922 and '033 patents (Sample No. 3).

Reference to FIGS. 13-14 show TGA data for anhydride cured reactionproducts of Sample Nos. 5, 55-58 and 59 (nopol epoxide glycidyl ether),having 80:20, 60:40, and 40:60 combinations of nopol epoxide glycidylether/RE-404-S, and RE-404-S, and anhydride cured reaction products ofnopol epoxide glycidyl ether (Sample No. 59), commercially availableepoxies ERL-4221 (Sample No. 4), and RE-404-S (Sample No. 5), andCompound XVI of the '922 and '033 patents (Sample Nos. 3).

The TGA data indicate that cured reaction products of the inventivecompositions (e.g., Sample Nos. 1-2, and 7-8) degrade and lose mass at atemperature lower than cured reaction products of the compositions basedon either of the commercially available epoxies, to which reference ismade above.

Practical reworkability was demonstrated using a hot air generator toheat the area around the die, fixed to the circuit board with thecompositions of Sample Nos. 17-25, 42-46 and 0.49, to an air temperatureof about 280° C., with a die temperature of about 215-220° C. for aperiod of time of about 1 to about 2 minutes. Then, the die may beeasily removed by pulling or twisting the die from the circuit boardusing tweezers in a period of time of about 20 to about 30 seconds. Thecircuit board may then be cleaned using a dremel at about 25,000 rpm,followed by application of a flat-end horse hair brush. The circuitboard cleaning ordinarily occurs within a period of time of about 2 toabout 3 minutes.

In addition, Sample Nos. 26-30 were reworked by localized heating to atemperature of about 100° C. for a period of time of about 60 minutes.Although reworkability data for these samples was observed, an increasedtemperature for a shortened time period would likely improve the dataobserved.

Thermosetting resin compositions prepared without limonene diepoxide,with the balance of the epoxy resin component from the RE-404-S epoxyresin (e.g., Sample Nos. 5 or 10), which was dispensed and cured asabove, do not allow for die removal in the manner so described.

The site of the failed semiconductor chip should then be fluxed and anew semiconductor chip may be attached using conventional flip chiptechnology. Then, the thermosetting resin composition of this inventionmay be applied around the periphary of the newly-replaced semiconductorchip and cured by heating to an appropriate temperature, as describedherein.

The samples described above are presented as illustrative, rather thanlimiting, examples of the inventive compositions. Many additionalembodiments thereof are included in the spirit and scope of theinvention, which is defined by the claims.

1. A thermosetting resin composition, said composition comprising: (a) acurable resin component, at least a portion of which is a compoundhaving at least one linkage selected from the group consisting ofoxiranes and thiiranes, substituted on at least three of thesubstitutable positions on the oxirane or thiirane carbons,respectively, with an alkyl, alkenyl or aryl substituent having a carboncontent of 1 to about twelve carbon atoms, with or without substitutionor interruption by one or more heteroatoms or halogens (I); and (b) acuring agent component selected from the group consisting of anhydridecompounds, amine compounds, amide compounds, imidazole compounds, andcombinations thereof, provided that the compound I does not include asits sole component an epoxy compound within any of the followingformulae [II:

II wherein each R is independently selected from the group consisting ofhydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl,C₁₋₄ alkoxy, halogen, cyano and nitro, R₁ and R₂ are each independentlyselected from the group consisting of hydrogen, methyl, ethyl, andpropyl, provided that both R₁ and R₂ cannot be hydrogen, and R₃ isindependently selected from propyl, and isopropyl, provided at least oneof R_(3a) and R_(3b), and at least one of R₃c and R_(3d) isindependently selected from the group consisting of methyl, ethyl,propyl, and isopropyl, and m is 0 or 1]

wherein each R is independently selected from the group consisting ofhydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert butyl,C₁₋₄ alkoxy, halogens, cyano, nitro, and phenyl, and R₃ and R₄ togetherform an epoxy group, and R₁ and R₂ are each independently selected fromthe group consisting of hydrogen, methyl, ethyl, propyl, and phenyl,except that at least one of R₁ and R₂ is not hydrogen, and n is 0 and pis 0 and m is 0 or 1, and the compounds are symmetrical;

wherein R, R¹, R², R³, and R⁴ are as defined above and m is 1 and p is 1and n is 1 or p is 0 and m is 0 and n is 1, and the compounds aresymmetrical;

wherein R is defined as above, and the compounds are symmetrical; and

wherein R, R₁ and R₂ are defined as above and c and d are both 1 or cand d are both 0, and the compounds are symmetrical, and whereinreaction products of the composition soften and lose their adhesivenessunder exposure to temperature conditions in excess of those used to curethe composition.
 2. (canceled)
 3. The composition according to claim 1,wherein the curable resin component includes a compound having at leastone oxirane linkage substituted on at least three of the substitutablepositions on the oxirane carbons with an alkyl, alkenyl or arylsubstituent having a carbon content of 1 to about twelve carbon atoms,with or without substitution or interuption by one or more heteroatomsor halogens.
 4. The composition according to claim 3, wherein thecompound having at least one oxirane linkage is a member selected fromthe group consisting of oxiranes prepared from2,10-dimethyl-6-methylene-4,8-bis(2-methyl-1-propenyl2,4,7,9-undecatetraene, 4-[(4E or 4Z)-1,5-dimethyl-4-heptenylidene oroctenylidene]-1-methyl-cyclohexene, 1,1′-[(1E or 1Z, 3E or3Z)-5-(1,1-dimethyl-2-propenyl)-3-(3-methyl-2-butenyl)-1,3-pentadiene-1,5-diyl]bis-benzene,4,6-dimethyl-[S or R-(E or Z, Z or E)]-2,5-octadiene,2,6,10,14-tetramethyl-7-(3-methyl-4-pentenyl)-2,5,9,13-pentadecatetraene,7-ethyl-3,11-dimethyl-(3Z or 3E, 6E or 6Z, 10Z or10E)-1,3,6,10-tridecatetraene, 3,4,8-trimethyl-1,4,7-nonatriene,13-ethyl-9-methyl-1,9,12-pentadecatetraene,1-methyl-4-(2-methyl-6-heptenylidene)-cyclohexene, 2,6,11-trimethyl-(Eor Z)-2,5,10-dodecatriene, 2,6-dimethyl-(E or Z, E orZ)-2,6,9-tetradecatriene, 7-(3-methyl-2-butenyl-(E or Z)-6-dodecene,6-(3-methyl-2-butenyl)-(E or Z)-6-dodecene,2,4,6,6,8-pentamethyl-2,4,7-nonatriene, 3,7-dimethyl-11-(methyl)-(E orZ, E or Z)-1,3,6,10-dodecatetraene,5-[3-methyl-1-(2-methyl-1-propenyl)-2-butenylidene]-1,3-cyclopentadiene,4-[(4E or 4Z)-1,5-dimethyl-4-heptenylidene]-1-methyl-(4Z or4E)-cyclohexene, 3,7,11-trimethyl-1,3,6,10-docosatetraene,3,7,11,15-tetramethyl-1,3,6,10-hexadecatetraene, 9-ethyl-2,6-dimethyl-(Eor Z, E or Z)-2,6,9-dodecatriene, 2-methyl-5-propyl-(E orZ)-2,5-nonadiene, 3,7,11-trimethyl-(Z or E, E or Z, E orZ)-1,3,6,10-dodecatetraene, 4,8,12-trimethyl-(Z or E, E or Z,E)-2,4,7,11-tridecatetraene, 1-methyl-4-(2-methyl-6-heptenylidene)-(E orZ)-cyclohexene, 3-ethyl-7,11-dimethyl-(E or Z, E or Z)-1, 3, 6,10-dodecatetraene,2,6,6,9-tetramethyl-7-(2-methyl-1-propenyl)-2,4,8-decatriene,2,7-dimethyl-4,5-bis(2-methyl-1-propenyl)-2,6-octadiene,3,7-dimethyl-1,3,6-octatriene,2-methyl-5-(1-methylethylidene)-cyclohexene,2,6-dimethyl-5-(1-methylethylidene)-1,3-cyclohexadiene,2,6-dimethyl-2,5-decadiene or octadiene,7-ethyl-3,11-dimethyl-1,3,6,10-dodecatetraene, 2-methyl-(E orZ)-2,5-octadiene, 7-ethyl-3,11-dimethyl-(E or Z, E orZ)-1,3,6,10-dodecatetraene, 2,7,11-trimethyl-(E orZ)-2,5,10-dodecatriene, 6,10-dimethyl-(Z or E, Z orE)-2,6,9-undecatrien-4-yne, 2,6-dimethyl-(Z or E)-2,5-dodecadiene,2,7-dimethyl-4,5-bis(2-methyl-1-propenyl)-2,4,6-octatriene,2,3,6,7-tetramethyl-1,3,6-octatriene, 2-methyl-5-propyl-(Z orE)-2,5-dodecadiene, 2-methyl-5-(1-methylethyl)-(E or Z)-2,5-dodecadiene,2-methyl-(Z or E)-2,5-dodecadiene, 2,4,4-trimethyl-(E orZ)-2,5-heptadiene, 2,6-dimethyl-2,5-octadiene, 3,4,7,11-tetramethyl-(Eor Z, Z or E)-1,3,6,10-dodecatraene, 3,7,11-trimethyl-(E or Z, E orZ)-1,3,6,10-dodecatetraene, 4,8-dimethyl-1,4,7-nonatriene,3,7,11,15-tetramethyl-1,3,6,10,14-hexadecapentaene, 2-methyl-(Z orE)-2,5-pentadecadiene, 2-methyl-5-(1-methylethylidene)-2-decene,2,6-dimethyl-2,5,7-decatriene, 4,8-dimethyl-2,4,7-nonatriene,15,19,23-trimethyl-15,18,22-heptatriacontatriene,8-(2-methyl-1-propenyl)-6-tetradecene, 3,7,11-trimethyl-(E orZ)-1,3,6,10-dodecatetraene,3,4-didehydro-2-(3-methyl-2-butenyl)-carotene,7-ethyl-3,11-dimethyl-1,3,6,10-dodecatetraene,1,3-dimethyl-4-propylidene-cyclopentene, 2,7,11-trimethyl-(E or Z, E orZ)-1,3,6,10-dodecatetraene, 6,10-dimethyl-1,4,6,9-undecatetraene,2-(1-methylethyl)-5-(1-methylethylidene)-1,3-cyclohexadiene,2-ethyl-5-ethylidene-cyclohexadiene,2-methyl-5-(1-methylethylidene)-1,3-cyclohexadiene, 3,7,10-trimethyl-(Zor E, E or Z)-1,3,6-undecatriene,4-(1,5-dimethyl-4-hexenylidene)-1-methyl-cyclohexene,1-methyl-4-(1-methylethylidene)-cyclohexene, 2,5-dimethyl-(Z orE)-2,5-heptadiene, 2-methyl-5-(1-methylethylidene)-1,3-cyclohexadiene,2,6,10-trimethyl-(E or Z, Z or E)-2,6,9-tetradecatriene, 6-methyl-(Z orE, E or Z)-2,5-dodecadiene, 2,3,6-trimethyl-(E or Z, E orZ)-1,3,6-octatriene,tetrahydro-3,7,11-trimethyl-1,3,6,10-dodecatetraene,3,4,7,11-tetramethyl-1,3,6,10-dodecatetraene, 3,4,7,11-tetramethyl-(Z orE, Z or E)-1,3,6,10-dodecatetraene,2,6-dimethyl-4-methylene-2,5-heptadiene,5-ethyl-2-methyl-2,5-heptadiene, 2,5-dimethyl-2,5-heptadiene oroctadiene, 3,7,11-trimethyl-dodecatriene, 2,4,6,6,8-pentamethyl-(E orZ)-2,4,7-nonatriene, 3,7-diethyl-11-methyl-1,3,6,10-tridecatetraene,7-ethyl-3,11-dimethyl-1,3,6,10-tridecatetraene, 2,6-dimethyl-(E orZ)-2,5-dodecadiene, 2,6,10-trimethyl-(E or Z, E orZ)-2,6,9-tetradecatriene, 3,7,11,15-tetramethyl-(Z or E, E or Z, E orZ)-1,3,6,10,14-hexadecapentaene, 3,7,11,15-tetramethyl-(3E or 3Z, 6E or6Z, 10E or 10Z)-1,3,6,10,14-hexadecapentaene,1-ethenyl-4-(1-methylethylidene)-cyclohexene,1-methyl-6-methylene-4-(1-methylethylidene)-cyclohexene,3,7,11-trimethyl-1,3,6-dodecatriene,4-(1,5-dimethylhexylidene)-1-methyl-cyclohexene,7-ethyl-3,11-dimethyl-(3Z or 3E, 6E or 6Z)-1,3,6,10-dodecatetraene,1,3,3′,4,4′,16-hexadehydro-1,2-dihydro-2,2′-bis-3-carotene, 7-methyl-(Zor E, Z or E)-3,6-dodecadiene, 6-ethylidene-2,3,10-trimethyl-(E or Z, Eor Z)-1,3,9-undecatriene, 2,3,6,7,10,11-hexamethyl-(E or Z, E orZ)-1,3,6,10-dodecatetraene, 2,3,6,7-tetramethyl-(E orZ)-1,3,6-octatriene, 2,7,11-trimethyl-1,3,6,11-dodecatetraene,3,7,11,15,19,23,27,31,35-nonamethyl-1,3,6,10,14,18,22,26,30,34-hexatriacontadecaene,2,6-dimethyl-9-propyl-2,6,9-tridecatriene, 3,6-dimethyl-(E or Z, E orZ)-1,3,6-octatriene, 3,7-diethyl-11-methyl-(3Z or 3E, 6E or 6Z)1,3,6,10-tridecatetraene, 7-ethyl-3,11-dimethyl-(3Z or 3E, 6E or6Z)-1,3,6,10-tridecatetraene, 1-methyl-4-(5-methyl-4-hexenylidene)-(4Eor 4Z)-cyclohexene, 2,6,10-trimethyl-(Z or E)-2,5,9-undecatriene,2,6,7,7-tetramethyl-(Z or E)-2,5-octadiene,2,6,10,11,11-pentamethyl-2,6,9-dodecatriene,2,6,10-trimethyl-2,6,9-tetradecatriene, 2,6-dimethyl-(Z orE)-2,5-decadiene, 6,10-dimethyl-1,6,9-undecatrien-4-yne,2,3,6-trimethyl-2,5-heptadiene, 2,4-dimethyl-(E or Z)-2,5-heptadiene,2,7,11-trimethyl-(E or Z, E or Z)-1,3,6,11-dodecatetraene,6-ethyl-3-methyl-2,5-decadiene, 2,6,10-trimethyl-(Z orE)-2,5-undecadiene, 3,7-dimethyl-3,6-octadien-1-yne,2,7,10-trimethyl-1,6,9-undecatriene, 4,5-dimethyl-(E or Z, E or Z, E orZ)-3,5,8-undecatriene, 4,5-dimethyl-2,5,8-undecatriene,1′-[4-methyl-2-(2-methyl-1-propenyl)-1,3-pentadienylidene]bis-benzene,1,4-(1,5-dimethyl-4-hexenylidene)-1-methyl-(4E or 4Z)-cyclohexene,2,6,11,15-tetramethyl-(Z or E)-2,6,9,14-hexadecatetraene,[3-methyl-1-(2-methyl-1-propenyl)-2-butenyl]-benzene,2,6,11-trimethyl-(E or Z, E or Z)-2,6,9-dodecatriene, 2,6-dimethyl-(E orZ, E or Z)-2,6,9-dodecatriene,2,3,6,7,10,11-hexamethyl-1,3,6,11-dodecatetraene,19-methyl-1-(2-methyl-1-2,4,6,8,10,12,14,16,18-eicosanonaenylium,17-methyl-1-(2-methyl-1-propenyl)-2,4,6,8,10,12,14,16-octadecaoctaenylium,15-methyl-1-(2-methyl-1-propenyl)-2,4,6,8,10,12,14-hexadecaheptaenylium,13-methyl-1-(2-methyl-1-propenyl)-2,4,6,8,10,12-tetradecahexaenylium,11-methyl-1-(2-methyl-1-propenyl)-2,4,6,8,10-dodecapentaenylium,9-methyl-1-(2-methyl-1-propenyl)-2,4,6,8-decatetraenylium,7-methyl-1-(2-methyl-1-propenyl)-2,4,6-octatrienylium,4,ethylidene-2,6-dimethyl-2,5-heptadiene, 3,7,11-trimethyl-(E orZ)-3,6,11-dodecatrien-1-yne, 3,7-dimethyl-(3E or 3Z)-3,6-octadien-1-yne,3,7-dimethyl-(E or Z)-3,6-nonadien-1-yne, 3,6,7-trimethyl-(E orZ)-3,6-octadien-1-yne, 7-ethyl-3-methyl-(E or Z)-3,6-nonadien-1-yne,3,7,11-trimethyl-(Z or E)-3,6,11-dodecatrien-1-yne,2,3,6,7,10,11-hexamethyl-1,3,6,11-dodecatetraene,2,6-dimethyl-2,5-heptadiene, 2-methyl-2,5-heptadiene,3,6,10-trimethyl-2,5,7,10-dodecatetraene,2,7,10-trimethyl-1,3,7,10-dodecatetraene, 3,6-dimethyl-1,3,6-octatriene,12-(2,2-dimethyl-6-methylenecyclohexyl)-3,8,8-trimethyl-11-methylene-(Eor Z)-(S)-1,3,6-dodecatriene, ocimene, 3,7,11-trimethyl-(3Z or 3E, 6Z or6E)-1,3,6,10-dodecatetraene, 2-methyl-4-methylene-2,5-heptadiene,3,8,8,14,18-pentamethyl-11-methylene-(E orZ)-1,3,6,13,17-nonadecapentaene, 2,7-dimethyl-2,5-octadiene,3,8,8,14,18-pentamethyl-11-methylene-(E or Z, E or Z, E orZ)-1,3,6,13,17-nonadecapentaene, 6,10-dimethyl-2,4,6,9-undecatetraene,2-methyl-(Z or E)-2,5-heptadiene, 2-methyl-(E or Z)-2,5-heptadiene,3,7-dimethyl-1,3,6-octatriene,4-(1,5-dimethyl-4-hexenylidene)-1-methyl-(4Z or 4E)-cyclohexene,2,6,10,14,19,22,27,31-octamethyl-2,6,10,14,16,18,22,26,30-dotriacontanonaene,2,6-dimethyl-2,5-heptadiene,4-(1,5-dimethyl-4-hexenylidene)-1-methyl-cyclohexene, 3,7-dimethyl-(3Eor 3Z)-1,3,6-octatriene,2,6,10,14,19,23,31-heptamethyl-2,5,10,14,16,18,22,26,29-dotriacontanonaene,3,7,dimethyl-(3Z or 3E)-1,3,6-octatriene,3-methyl-1-(2-methyl-1-propenyl-(E or Z)-2-pentenyl,2,6-dimethyl-4-(2-methylpropenyl)-1,3,5-heptatriene,2,6-dimethyl-4-methylene-2,5-heptadiene,1-methyl-4-(1-methylethylidene)-cyclohexene, 3,7,11-trimethyl-(3E or 3Z,6E or 6Z)-1,3,6,10-dodecatetraene,4-(1,5-dimethyl-4-hexenylidene)-1-methyl-cyclohexene, isoprene, myrcene,dihydromyrene, linalool, terpinenes (α, β, and γ), limonene,terpinolene, menthadiene (p-3,8 or p-2,4), geraniol, nerol,geranylacetate, neryl acetate, nerolidol, farnesol, dehydronerolidol,α-bisabolol, valancene, nookatene, nootkatone,dimethyl-2,4,6-octratriene, β-phellandrences, piperitols (−, cis and +,trans), 1-methyl-1,4-cyclohexadiene, methyl cyclopentadiene dimer,ethylidene norbornene, dipentene, carvestrene, carvone (− or +),alloocimenes (4-trans-6-cis and 4-trans-6-trans), alloocimenols,ionomers, guaiazulene, lanosterol, squalene, lycopene, carotenes (β andγ), nopol glycidyl ether, and combinations thereof.
 5. The compositionaccording to claim 3, wherein the compound having at least one oxiranelinkage is a member selected from the group consisting of limonenediepoxide, gamma-terpinene diepoxide, methyl cyclopentadiene diepoxidedimer, ethylidene norbornene diepoxide, nopol epoxide glycidyl ether andcombinations thereof.
 6. The composition according to claim 1, whereinthe anhydride component of the curing agent component is selected fromthe group consisting of hexahydrophthalic anhydride, methylhexahydrophthalic anhydride,5-(2,5-dioxotetrahydrol)-3-methyl-3-cyclohexene-1,2-dicarboxylicanhydride, and combinations thereof.
 7. The composition according toclaim 1, wherein the amine compounds of the curing agent component isselected from the group consisting of 1,5-diazabiyclo [4.3.0]non-5-ene;1,8-diazabiylo[5.4.0]undec-7-ene; 1,5,7-triazabicyclo [4.4.0]dec-5-ene;quinuclidine; 1,4-diazabicyclo[2.2.2.]octane; and combinations thereof.8. (canceled)
 9. The composition according to claim 1, wherein theimidazole compounds of the curing agent component is selected from thegroup consisting of imidazole, isoimidazole, 2-methyl imidazole,2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, butylimidazole,2-heptadecenyl-4-methylimidazole, 2-undecenylimidazole,1-vinyl-2-methylimidazole, 2-n-heptadecylimidazole, 2-undecylimidazole,2-heptadecylimidazole, 1-benzyl-2-methylimidazole,1-propyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole,1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole,1-cyanoethyl-2-phenylimidazole, 1-guanaminoethyl-2-methylimidazole,addition products of an imidazole and trimellitic acid, additionproducts of an imidazole and 2-n-heptadecyl-4-methylimidazole,phenylimidazole, benzylimidazole, 2-methyl-4,5-diphenylimidazole,2,3,5-triphenylimidazole, 2-styrylimidazole, 1-(dodecylbenzyl)-2-methylimidazole,2-(2-hydroxyl-4-t-butylphenyl)-4,5-diphenylimidazole,2-(2-methoxyphenyl)-4,5-diphenylimidazole,2-(3-hydroxyphenyl)-4,5-diphenylimidazole,2-(p-dimethylaminophenyl)-4,5-diphenylimidazole,2-(2-hydroxyphenyl)-4,5-diphenylimidazole,di(4,5-diphenyl-2-imidazole)-benzene-1,4,2-naphthyl-4,5-diphenylimidazole,1-benzyl-2-methylimidazole, 2-p-methoxystyrylimidazole, and combinationsthereof.
 10. The composition according to claim 1, wherein the curingagent component is used in an amount of from about 1 to about 100 weightpercent, based on the weight of the curable resin component.
 11. Thecomposition according to claim 1, further comprising an inorganic fillercomponent.
 12. The composition according to claim 11, wherein theinorganic filler component is selected from the group consisting ofmaterials constructed of or containing reinforcing silicas, aluminumoxide, silicon nitride, aluminum nitride, silica-coated aluminumnitride, boron nitride, and combinations thereof.
 13. The compositionaccording to claim 11, wherein the inorganic filler component has a lowion concentration and a particle size in the range of about 2-10microns. 14-18. (canceled)
 19. The composition according to claim 1,further comprising a cyanate ester.
 20. The composition according toclaim 19, wherein the cyanate ester is a member selected from the groupconsisting of dicyanatobenzenes, tricyanatobenzenes,dicyanatonaphthalenes, tricyanatonaphthalenes, dicyanato-biphenyl,bis(cyanatophenyl)methanes and alkyl derivatives thereof,bis(dihalocyanatophenyl)propanes, bis(cyanatophenyl)ethers,bis(cyanatophenyl)sulfides, bis(cyanatophenyl)propanes,tris(cyanatophenyl)phosphites, tris(cyanatophenyl)phosphates,bis(halocyanatophenyl)methanes, cyanated novolac,bis[cyanatophenyl(methylethylidene)]benzene, cyanatedbisphenol-terminated thermoplastic oligomers, and combinations thereof.21. The composition according to claim 1, sealing underfilling between asemiconductor device including a semiconductor chip mounted on a carriersubstrate and a circuit board to which the semiconductor device iselectrically connected.
 22. The composition according to claim 1,sealing underfilling between a semiconductor device including asemiconductor chip mounted on a carrier substrate and a circuit board towhich the semiconductor device is electrically connected, wherein thecurable resin component is present in an amount within the range ofabout 10 to 70 weight percent, based on the total weight of thecomposition; the curing agent component is present in an amount withinthe range of 1 to about 100 weight percent, based on the weight of thecurable resin component; and further comprising an inorganic fillercomponent in an amount up to about 70 weight percent, based on the totalweight of the composition; and a flowability agent in an amount up toabout 2 weight percent, based on the weight of the composition.
 23. Thecomposition according to claim 1, wherein the curable resin componentincludes a compound having at least one thiirane linkage substituted onat least three of the substitutable positions on the thiirane carbonswith an alkyl, alkenyl or aryl substituent having a carbon content of 1to about twelve carbon atoms, with or without substitution orinterruption by one or more heteroatoms or halogens.
 24. The compositionaccording to claim 23, wherein the compound having at least one thiiranelinkage is a member selected from the group consisting of thiiranesprepared from 2,10-dimethyl-6-methylene-4,8-bis(2-methyl-1-propenyl2,4,7,9-undecatetraene, 4-[(4E or 4Z)-1,5-dimethyl-4-heptenylidene oroctenylidene]-1-methyl-cyclohexene, 1,1′-[(1E or 1Z, 3E or3Z)-5-(1,1-dimethyl-2-propenyl)-3-(3-methyl-2-butenyl)-1,3-pentadiene-1,5-diyl]bis-benzene,4,6-dimethyl-[S or R-(E or Z, Z or E)]-2,5-octadiene,2,6,10,14-tetramethyl-7-(3-methyl-4-pentenyl)-2,5,9,13-pentadecatetraene,7-ethyl-3,11-dimethyl-(3Z or 3E, 6E or 6Z, 10Z or10E)-1,3,6,10-tridecatetraene, 3,4,8-trimethyl-1,4,7-nonatriene,13-ethyl-9-methyl-1,9,12-pentadecatetraene,1-methyl-4-(2-methyl-6-heptenylidene)-cyclohexene, 2,6,11-trimethyl-(Eor Z)-2,5,10-dodecatriene, 2,6-dimethyl-(E or Z, E orZ)-2,6,9-tetradecatriene, 7-(3-methyl-2-butenyl-(E or Z)-6-dodecene,6-(3-methyl-2-butenyl)-(E or Z)-6-dodecene,2,4,6,6,8-pentamethyl-2,4,7-nonatriene, 3,7-dimethyl-11-(methyl)-(E orZ, E or Z)-1,3,6,10-dodecatetraene,5-[3-methyl-1-(2-methyl-1-propenyl)-2-butenylidene]-1,3-cyclopentadiene,4-[(4E or 4Z)-1,5-dimethyl-4-heptenylidene]-1-methyl-(4Z or4E)-cyclohexene, 3,7,11-trimethyl-1,3,6,10-docosatetraene,3,7,11,15-tetramethyl-1,3,6,10-hexadecatetraene, 9-ethyl-2,6-dimethyl-(Eor Z, E or Z)-2,6,9-dodecatriene, 2-methyl-5-propyl-(E orZ)-2,5-nonadiene, 3,7,11-trimethyl-(Z or E, E or Z, E orZ)-1,3,6,10-dodecatetraene, 4,8,12-trimethyl-(Z or E, E or Z,E)-2,4,7,11-tridecatetraene, 1-methyl-4-(2-methyl-6-heptenylidene)-(E orZ)-cyclohexene, 3-ethyl-7,11-dimethyl-(E or Z, E or Z)-1, 3, 6,10-dodecatetraene,2,6,6,9-tetramethyl-7-(2-methyl-1-propenyl)-2,4,8-decatriene,2,7-dimethyl-4,5-bis(2-methyl-1-propenyl)-2,6-octadiene,3,7-dimethyl-1,3,6-octatriene,2-methyl-5-(1-methylethylidene)-cyclohexene,2,6-dimethyl-5-(1-methylethylidene)-1,3-cyclohexadiene,2,6-dimethyl-2,5-decadiene or octadiene,7-ethyl-3,11-dimethyl-1,3,6,10-dodecatetraene, 2-methyl-(E orZ)-2,5-octadiene, 7-ethyl-3,11-dimethyl-(E or Z, E orZ)-1,3,6,10-dodecatetraene, 2,7,11-trimethyl-(E orZ)-2,5,10-dodecatriene, 6,10-dimethyl-(Z or E, Z orE)-2,6,9-undecatrien-4-yne, 2,6-dimethyl-(Z or E)-2,5-dodecadiene,2,7-dimethyl-4,5-bis(2-methyl-1-propenyl)-2,4,6-octatriene,2,3,6,7-tetramethyl-1,3,6-octatriene, 2-methyl-5-propyl-(Z orE)-2,5-dodecadiene, 2-methyl-5-(1-methylethyl)-(E or Z)-2,5-dodecadiene,2-methyl-(Z or E)-2,5-dodecadiene, 2,4,4-trimethyl-(E orZ)-2,5-heptadiene, 2,6-dimethyl-2,5-octadiene, 3,4,7,11-tetramethyl-(Eor Z, Z or E)-1,3,6,10-dodecatraene, 3,7,11-trimethyl-(E or Z, E orZ)-1,3,6,10-dodecatetraene, 4,8-dimethyl-1,4,7-nonatriene,3,7,11,15-tetramethyl-1,3,6,10,14-hexadecapentaene, 2-methyl-(Z orE)-2,5-pentadecadiene, 2-methyl-5-(1-methylethylidene)-2-decene,2,6-dimethyl-2,5,7-decatriene, 4,8-dimethyl-2,4,7-nonatriene,15,19,23-trimethyl-15,18,22-heptatriacontatriene,8-(2-methyl-1-propenyl)-6-tetradecene, 3,7,11-trimethyl-(E orZ)-1,3,6,10-dodecatetraene,3,4-didehydro-2-(3-methyl-2-butenyl)-carotene,7-ethyl-3,11-dimethyl-1,3,6,10-dodecatetraene,1,3-dimethyl-4-propylidene-cyclopentene, 2,7,11-trimethyl-(E or Z, E orZ)-1,3,6,10-dodecatetraene, 6,10-dimethyl-1,4,6,9-undecatetraene,2-(1-methylethyl)-5-(1-methylethylidene)-1,3-cyclohexadiene,2-ethyl-5-ethylidene-cyclohexadiene,2-methyl-5-(1-methylethylidene)-1,3-cyclohexadiene, 3,7,10-trimethyl-(Zor E, E or Z)-1,3,6-undecatriene,4-(1,5-dimethyl-4-hexenylidene)-1-methyl-cyclohexene,1-methyl-4-(1-methylethylidene)-cyclohexene, 2,5-dimethyl-(Z orE)-2,5-heptadiene, 2-methyl-5-(1-methylethylidene)-1,3-cyclohexadiene,2,6,10-trimethyl-(E or Z, Z or E)-2,6,9-tetradecatriene, 6-methyl-(Z orE, E or Z)-2,5-dodecadiene, 2,3,6-trimethyl-(E or Z, E orZ)-1,3,6-octatriene,tetrahydro-3,7,11-trimethyl-1,3,6,10-dodecatetraene,3,4,7,11-tetramethyl-1,3,6,10-dodecatetraene, 3,4,7,11-tetramethyl-(Z orE, Z or E)-1,3,6,10-dodecatetraene,2,6-dimethyl-4-methylene-2,5-heptadiene,5-ethyl-2-methyl-2,5-heptadiene, 2,5-dimethyl-2,5-heptadiene oroctadiene, 3,7,11-trimethyl-dodecatriene, 2,4,6,6,8-pentamethyl-(E orZ)-2,4,7-nonatriene, 3,7-diethyl-11-methyl-1,3,6,10-tridecatetraene,7-ethyl-3,11-dimethyl-1,3,6,10-tridecatetraene, 2,6-dimethyl-(E orZ)-2,5-dodecadiene, 2,6,10-trimethyl-(E or Z, E orZ)-2,6,9-tetradecatriene, 3,7,11,15-tetramethyl-(Z or E, E or Z, E orZ)-1,3,6,10,14-hexadecapentaene, 3,7,11,15-tetramethyl-(3E or 3Z, 6E or6Z, 10E or 10Z)-1,3,6,10,14-hexadecapentaene,1-ethenyl-4-(1-methylethylidene)-cyclohexene,1-methyl-6-methylene-4-(1-methylethylidene)-cyclohexene,3,7,11-trimethyl-1,3,6-dodecatriene,4-(1,5-dimethylhexylidene)-1-methyl-cyclohexene,7-ethyl-3,11-dimethyl-(3Z or 3E, 6E or 6Z)-1,3,6,10-dodecatetraene,1,3,3′,4,4′,16-hexadehydro-1,2-dihydro-2,2′-bis-3-carotene, 7-methyl-(Zor E, Z or E)-3,6-dodecadiene, 6-ethylidene-2,3,10-trimethyl-(E or Z, Eor Z)-1,3,9-undecatriene, 2,3,6,7,10,11-hexamethyl-(E or Z, E orZ)-1,3,6,10-dodecatetraene, 2,3,6,7-tetramethyl-(E orZ)-1,3,6-octatriene, 2,7,11-trimethyl-1,3,6,11-dodecatetraene,3,7,11,15,19,23,27,31,35-nonamethyl-1,3,6,10,14,18,22,26,30,34-hexatriacontadecaene,2,6-dimethyl-9-propyl-2,6,9-tridecatriene, 3,6-dimethyl-(E or Z, E orZ)-1,3,6-octatriene, 3,7-diethyl-11-methyl-(3Z or 3E, 6E or 6Z)1,3,6,10-tridecatetraene, 7-ethyl-3,11-dimethyl-(3Z or 3E, 6E or6Z)-1,3,6,10-tridecatetraene, 1-methyl-4-(5-methyl-4-hexenylidene)-(4Eor 4Z)-cyclohexene, 2,6,10-trimethyl-(Z or E)-2,5,9-undecatriene,2,6,7,7-tetramethyl-(Z or E)-2,5-octadiene,2,6,10,11,11-pentamethyl-2,6,9-dodecatriene,2,6,10-trimethyl-2,6,9-tetradecatriene, 2,6-dimethyl-(Z orE)-2,5-decadiene, 6,10-dimethyl-1,6,9-undecatrien-4-yne,2,3,6-trimethyl-2,5-heptadiene, 2,4-dimethyl-(E or Z)-2,5-heptadiene,2,7,11-trimethyl-(E or Z, E or Z)-1,3,6,11-dodecatetraene,6-ethyl-3-methyl-2,5-decadiene, 2,6,10-trimethyl-(Z orE)-2,5-undecadiene, 3,7-dimethyl-3,6-octadien-1-yne,2,7,10-trimethyl-1,6,9-undecatriene, 4,5-dimethyl-(E or Z, E or Z, E orZ)-3,5,8-undecatriene, 4,5-dimethyl-2,5,8-undecatriene,1′-[4-methyl-2-(2-methyl-1-propenyl)-1,3-pentadienylidene]bis-benzene,1,4-(1,5-dimethyl-4-hexenylidene)-1-methyl-(4E or 4Z)-cyclohexene,2,6,11,15-tetramethyl-(Z or E)-2,6,9,14-hexadecatetraene,[3-methyl-1-(2-methyl-1-propenyl)-2-butenyl]-benzene,2,6,11-trimethyl-(E or Z, E or Z)-2,6,9-dodecatriene, 2,6-dimethyl-(E orZ, E or Z)-2,6,9-dodecatriene,2,3,6,7,10,11-hexamethyl-1,3,6,11-dodecatetraene,19-methyl-1-(2-methyl-1-2,4,6,8,10,12,14,16,18-eicosanonaenylium,17-methyl-1-(2-methyl-1-propenyl)-2,4,6,8,10,12,14,16-octadecaoctaenylium,15-methyl-1-(2-methyl-1-propenyl)-2,4,6,8,10,12,14-hexadecaheptaenylium,13-methyl-1-(2-methyl-1-propenyl)-2,4,6,8,10,12-tetradecahexaenylium,11-methyl-1-(2-methyl-1-propenyl)-2,4,6,8,10-dodecapentaenylium,9-methyl-1-(2-methyl-1-propenyl)-2,4,6,8-decatetraenylium,7-methyl-1-(2-methyl-1-propenyl)-2,4,6-octatrienylium,4,ethylidene-2,6-dimethyl-2,5-heptadiene, 3,7,11-trimethyl-(E orZ)-3,6,11-dodecatrien-1-yne, 3,7-dimethyl-(3E or 3Z)-3,6-octadien-1-yne,3,7-dimethyl-(E or Z)-3,6-nonadien-1-yne, 3,6,7-trimethyl-(E orZ)-3,6-octadien-1-yne, 7-ethyl-3-methyl-(E or Z)-3,6-nonadien-1-yne,3,7,11-trimethyl-(Z or E)-3,6,11-dodecatrien-1-yne,2,3,6,7,10,11-hexamethyl-1,3,6,11-dodecatetraene,2,6-dimethyl-2,5-heptadiene, 2-methyl-2,5-heptadiene,3,6,10-trimethyl-2,5,7,10-dodecatetraene,2,7,10-trimethyl-1,3,7,10-dodecatetraene, 3,6-dimethyl-1,3,6-octatriene,12-(2,2-dimethyl-6-methylenecyclohexyl)-3,8,8-trimethyl-11-methylene-(Eor Z)-(S)-1,3,6-dodecatriene, ocimene, 3,7,11-trimethyl-(3Z or 3E, 6Z or6E)-1,3,6,10-dodecatetraene, 2-methyl-4-methylene-2,5-heptadiene,3,8,8,14,18-pentamethyl-11-methylene-(E orZ)-1,3,6,13,17-nonadecapentaene, 2,7-dimethyl-2,5-octadiene,3,8,8,14,18-pentamethyl-11-methylene-(E or Z, E or Z, E orZ)-1,3,6,13,17-nonadecapentaene, 6,10-dimethyl-2,4,6,9-undecatetraene,2-methyl-(Z or E)-2,5-heptadiene, 2-methyl-(E or Z)-2,5-heptadiene,3,7-dimethyl-1,3,6-octatriene,4-(1,5-dimethyl-4-hexenylidene)-1-methyl-(4Z or 4E)-cyclohexene,2,6,10,14,19,22,27,31-octamethyl-2,6,10,14,16,18,22,26,30-dotriacontanonaene,2,6-dimethyl-2,5-heptadiene,4-(1,5-dimethyl-4-hexenylidene)-1-methyl-cyclohexene, 3,7-dimethyl-(3Eor 3Z)-1,3,6-octatriene,2,6,10,14,19,23,31-heptamethyl-2,5,10,14,16,18,22,26,29-dotriacontanonaene,3,7,dimethyl-(3Z or 3E)-1,3,6-octatriene,3-methyl-1-(2-methyl-1-propenyl-(E or Z)-2-pentenyl,2,6-dimethyl-4-(2-methylpropenyl)-1,3,5-heptatriene,2,6-dimethyl-4-methylene-2,5-heptadiene,1-methyl-4-(1-methylethylidene)-cyclohexene, 3,7,11-trimethyl-(3E or 3Z,6E or 6Z)-1,3,6,10-dodecatetraene,4-(1,5-dimethyl-4-hexenylidene)-1-methyl-cyclohexene, isoprene, myrcene,dihydromyrene, linalool, terpinenes (α, β, and γ), limonene,terpinolene, menthadiene (p-3,8 or p-2,4), geraniol, nerol,geranylacetate, neryl acetate, nerolidol, farnesol, dehydronerolidol,α-bisabolol, valancene, nookatene, nootkatone,dimethyl-2,4,6-octratriene, β-phellandrences, piperitols (−, cis and +,trans), 1-methyl-1,4-cyclohexadiene, methyl cyclopentadiene dimer,ethylidene norbornene, dipentene, carvestrene, carvone (− or +)alloocimenes (4-trans-6-cis and 4-trans-6-trans), alloocimenols,ionomers, guaiazulene, lanosterol, squalene, lycopene, carotenes (β andγ), nopol glycidyl ether, and combinations thereof.
 25. The compositionsaccording to claim 1, wherein the thiirane compound is a member selectedfrom the group consisting of thiiranes prepared from limonene,terpinene, nopol, ethylidene norbornene, methyl cyclopentadiene dimer,and combinations thereof. 26-30. (canceled)
 31. Reaction products formedfrom the compositions according to claim
 1. 32-39. (canceled)